CN103998985A - Large phase shift mask and method for manufacturing phase shift mask - Google Patents

Large phase shift mask and method for manufacturing phase shift mask Download PDF

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Publication number
CN103998985A
CN103998985A CN201280062178.8A CN201280062178A CN103998985A CN 103998985 A CN103998985 A CN 103998985A CN 201280062178 A CN201280062178 A CN 201280062178A CN 103998985 A CN103998985 A CN 103998985A
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Prior art keywords
phase shift
region
mentioned
translucent
exposure
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CN201280062178.8A
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CN103998985B (en
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木下一树
飞田敦
二岛悟
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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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
    • 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
    • G03F1/32—Attenuating PSM [att-PSM], e.g. halftone PSM or PSM having semi-transparent phase shift portion; Preparation thereof
    • 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
    • G03F1/54—Absorbers, e.g. of opaque materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

Provided are the structure of a semi-transparent phase shift mask that is suitable for forming a precise pattern in a large photomask used for manufacturing a liquid crystal panel or an EL panel, and the method for manufacturing the same. Further, provided is a structure for minimizing the occurrence of a side peak which is created when a pattern is exposed using a semi-transparent phase shift mask. In a pattern in which transmission regions are arranged next to both sides of the semi-transparent phase shift region that is formed on a transparent substrate, the luminous transmittance of the semi-transparent phase shift region is set within the range of 4 to 30% and the width thereof is set within the range of 1 to 5 [mu]m, thereby improving the contrast of an exposure intensity distribution while minimizing the occurrence of a side peak.

Description

The manufacture method of large-scale phase-shift mask and large-scale phase-shift mask
Technical field
The present invention relates to a kind of photomask, relate in particular to a kind of large-scale photomask using and the manufacture method of large-scale photomask in the manufacture of active matrix (active matrix) the formula display devices such as liquid crystal display, electroluminescence (EL, ElectroLuminescence) display device.
Background technology
The variation of the specification of the photomask using in the manufacture of flat-panel monitor (brief note is FPD (Flat Panel Display)) is that large screen and the fine in the slim TV there to be liquid crystal display (LCD (brief note is as Liquid Crystal Display)) in use, observed turn to representative.About large screen, about the nineteen ninety starting in the volume production of the slim TV of liquid crystal for the manufacture of in the glass substrate that is called 1st generation be of a size of 300mm × 400mm, about 2002 start for the manufacture of in the 5th generation glass substrate be of a size of 1100mm × 1300mm, about 2006 start for the manufacture of in the 8th generation glass substrate size reach 2140mm × 2460mm.
The high-precision refinement of liquid crystal display is to develop to some extent at personal computer high pixelation in display at first.Video Graphics Array (VGA, Video Graphics Array) display is 640 × 480 pixels, XGA (Extended Graphics Array) (XGA, Extended Graphics Array) display is 1024 × 768 pixels, at super XGA (Extended Graphics Array) (sXGA, Super Extended Graphics Array) be 1280 × 1024 pixels in display, ultra extended graphics array (UXGA, Ultra Extended Graphics Array) display is 1600 × 1200 pixels.Follow this contour pixelation, pel spacing also develops into 0.24mm, 0.20mm and constantly miniaturization from 0.33mm.And then, in intelligent mobile phone (smart phone) etc., in 4.5 types, be 1280 × 720 pixels, pel spacing reaches 0.077mm (329ppi).Again, hd-tv (HDTV, High Definition Television) be 1920 × 1080 pixels, also having further interpolated pixel and making pixel count is the display of 3840 × 2160 pixels of 4 times (being called 4K liquid crystal panel) of HDTV.
Below the photomask of manufacturing the exposure device of liquid crystal display as above, use in exposure device is described.That liquid crystal is enclosed between the colored filter of manufacturing respectively and tft array substrate and form as the unit of colorful film transistor (TFT, the Thin Film Transistor) liquid crystal display of representative liquid crystal display.And then, in liquid crystal display, pack into signal of video signal is converted to the driving signal of TFT peripheral driving circuit and the backlight of being supplied with, and make LCD MODULE.
The pattern using in each step of tft array substrate manufacturing step is that to utilize multiplying power be that large-scale mask doubly such as 1 to 1 grade is waiting in projection type exposure device (being also called projection aligner) doubly and exposes and form.At present, projection exposure mode doubly such as the grade of utilizing this large-scale mask becomes productivity well and accurately tft array substrate is carried out the manufacture method of the standard of pattern formation.Moreover, in the pattern of colored filter forms, the manufacture method that favourable proximity printing mode is standard aspect cost.Proximity printing is that mask and exposure object are approached to configuration with the gap of tens of μ m～100 μ m left and right, and irradiates the Exposure mode of directional light from the rear of mask.
The large-scale mask that tft array substrate is used starts with the size of 350mm × 350mm at first, constantly in large size along with the maximization of the grade using in the manufacture of tft array substrate projection type exposure device doubly.At the grade of the manufacture for tft array substrate projection type exposure device doubly, there is the mirror surface projection Exposure mode for the pattern projection exposure of mask is used to mirror system to workpiece and use 2 kinds of lens projection exposure mode of lens combination.According to the specification of each exposure device, the size difference of the large-scale mask using, for the 5th generation glass substrate, in mirror surface projection Exposure mode, use the large-scale mask of the size of 520mm × 610mm, in lens projection exposure mode, use the large-scale mask of the size of 800mm × 920mm.And then, for the 8th generation glass substrate, in mirror surface projection Exposure mode, use the large-scale mask of the size of 850mm × 1400mm, in lens projection exposure mode, use the large-scale mask of the size of 1220mmx1400mm.In this case, be by one side for photomask more than 350mm is made as large-scale mask.
Cornerwise length of the mask (6 inches of photomasks) that common semiconductor is used is about 215mm, on the other hand, cornerwise length of above-mentioned large-scale mask is 495mm in 1st generation mask, in the mirror surface projection Exposure mode in the 5th generation, be about 801mm, in the lens projection exposure mode in the 8th generation by large-scale medium-and-large-sizedization of mask to 1856mm.
As mentioned above, the large-scale mask forming for the pattern of tft array substrate is that the mask of using with respect to semiconductor crystal wafer is expressed as the size of 2.3 times to 8.6 times with the ratio of cornerwise length.And then drawing the Area Ratio directly related with manufacturing cost such as time, supervision time is 4.4 times to 72 times.According to the requirement of therefore planting the cost aspect that large scale produces, large-scale mask had been previously binary mask (binary mask), and layer structure comprises 2 layers that are layered in the photomask taking chromium as major component on quartz glass and are layered in the anti-reflective film taking chromium oxide or nitrogen chromium oxide as major component on photomask.Moreover the transmittance under the exposure wavelength of the photomask of the large-scale binary mask of needs is below 0.1% and the reflectivity of anti-reflective film is the performance below 30%.
As mentioned above, tft array substrate maximizes, and on the other hand, requires in recent years the miniaturization of pattern., require fine pattern imaging equably in the entirety of exposure area of the resolution limit that approaches exposure device.Especially the photomask that the gate electrode of tft array substrate and source drain electrode, contact hole are used requires the miniaturization of pattern.But the numerical aperture of the lens combination of the large-scale projection aligner using in the manufacture of liquid crystal panel is less is 0.1 left and right, the limit of resolution is also 3.0 μ m, thereby has the limit in the formation of fine pattern.
If use fine line and gap (L/S below the resolution limit that is formed with exposure device, line and space) photomask of binary form of pattern exposes to resist, at imaging surface, the amplitude of the exposure intensity corresponding with the part of the line (shading) on photomask and the part of gap (seeing through) is less, the exposure of the part corresponding with gap (seeing through) portion does not reach the threshold value of the sensitivity of resist, result, even if make resist development, also cannot form pattern.
As one of the solution of the prior art for above-mentioned problem, in patent documentation 1 (Japanese Patent Laid-Open 2009-4242753 communique), propose to have the method that uses gray tone mask.The Fig. 8 that schematically shows exposure light amount distribution that utilizes Fig. 7 of the Fig. 1 recording in referenced patents document 1 and append for key diagram 7 describes.
As illustrated in Fig. 7 (a), in prior art, illustrative photomask 70 is on transparency carrier 71, to be formed with light shielding part 74 that utilization do not have the photomask 72 of fine pattern, to utilize the semi light transmitting part 75 of the semi-transparent film 73 without fine pattern, the fine pattern portion 76 (comprise transmittance section and utilize the semi light transmitting part of semi-transparent film 73) that utilizes semi-transparent film 73,4 regions of transmittance section 77 (transparency carrier 71 exposes).
If utilize in above-mentioned prior art illustrative photomask 70 and exposure light 5 to expose, photoresistance film 83 by pattern transfer to the eurymeric on transfer printing body 80, as shown in Fig. 7 (b), on transfer printing body 80, form the residual diaphragm area 83b of the residual diaphragm area 83a, the film that comprise the thick film after development, the fine pattern region 83c corresponding with fine pattern portion 76 on above-mentioned photomask 70 and in fact without the pattern transferring (photoresistance pattern) of the region 83d of residual film.Moreover symbol 82a, the 82b in Fig. 7 represents the film on substrate 81 that is layered in transfer printing body 80.
In Fig. 8, illustrate and illustrate that half sees through the effect of the fine pattern 76 of film.; as common binary mask; the distribution shape 84c of the exposure light amount when utilizing photomask to form the situation of fine pattern; because pattern is not separated picture under micro situation; even if so in the peak value part of the exposure corresponding with transmittance section; also do not reach the exposure 85 that eurymeric resist comes off, and do not form pattern (Fig. 8 (b)).On the other hand, have that half photomask 70 that sees through the fine pattern 76 of film exposes and when the situation of transfer printing, the light transmission capacity of exposure light is greater than the light transmission capacity of the exposure light amount of the fine pattern portion of the photomask that utilizes common binary mask in utilization.Therefore, the distribution shape 83c of the exposure light amount while utilizing half situation through film formation fine pattern reaches in the part of the peak value of the exposure corresponding with transmittance section the exposure 85 that eurymeric resist comes off, even if be fine pattern, also can obtain sufficient exposure and pattern 83c is formed on to (Fig. 8 (a)) on resist.
On the other hand, using the photomask 70 of this kind of prior art and during by the fine pattern 76 of exposure transfer printing semi-transparent film 73, the light transmission capacity of exposure light is greater than the light transmission capacity of the exposure light amount of the light-shielding pattern portion of the photomask that utilizes common binary mask, and the contrast that exposure light amount distributes reduces.Therefore the residual film value of photoresistance of the corresponding residual diaphragm area 83a of thick film when the residual film value of photoresistance of the fine pattern region 83c on transfer printing body when, transfer printing utilization half sees through the situation of fine pattern portion 76 of film is less than with the situation of the common photomask pattern of transfer printing.Therefore, for the etch process of the transfer printing body after suitably carrying out, and the essential exposure of adjusting is adjusted the condition in the developing manufacture process of the resist after exposure subtly simultaneously, and the residual film value of the photoresistance that preferably regulates fine pattern region 83c, and become the main cause of the transfer step difficulty that causes exposing.Above, be illustrated as an example of eurymeric resist example, in the time of the situation of negative resist, also need equally the meticulous adjustment of exposure imaging condition.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2009-42753 communique
Summary of the invention
The problem that invention will solve
As mentioned above, the maximization development of the photomask using in the manufacture of the flat-panel monitor taking liquid crystal display as representative, on the other hand, the miniaturization development of the display pixel pitch of flat-panel monitor, the requirement of the miniaturization of the pattern transferring to photomask also smartens.
Problem of the present invention is to provide a kind of large-scale projection aligner in the manufacture by for display panels by pattern transfer during to transfer printing body, the contrast that improves the exposure light amount distribution of the fine pattern on imaging surface is carried out the phase-shift mask of the structure of the applicable large-scale photomask of transfer printing, and its manufacture method is provided simultaneously.
For the means of dealing with problems
(the 1st means)
The 1st means of the present invention are that a kind of large-scale phase-shift mask is (following, there is the situation describing referred to as phase-shift mask), it comprises transparency carrier, and it is (following to be formed on translucent translucent phase shift film on above-mentioned transparency carrier, there is the situation describing referred to as phase shift film), and comprise the region that sees through of having exposed above-mentioned transparency carrier, and the translucent phase shift region that is only provided with above-mentioned phase shift film on above-mentioned transparency carrier is (following, there is the situation describing referred to as phase shift region), and comprise and dispose adjacently the above-mentioned mask pattern that sees through region and above-mentioned translucent phase shift region, and see through the phase place of exposure light in above-mentioned translucent phase shift region with respect to seeing through the above-mentioned phase reversal of exposure light that sees through region, in the time that the transmittance of the above-mentioned exposure light that sees through region is made as to 100%, the transmittance of the exposure light in above-mentioned translucent phase shift region is the value of 4% to 30% scope.
By the phase-shift mask of structure that uses above-mentioned the 1st means, can easily make the large-scale mask that fine pattern is improved to the contrast of exposing patterns.And then, if the transmittance of the exposure light in above-mentioned translucent phase shift region is less than 4%, utilize the effect of phase shift raising contrast less, if the transmittance of the exposure light in above-mentioned translucent phase shift region is greater than 30%, shade function deficiency, and produce the possibility of the resist sensitization of translucent phase shift region entirety.
(the 2nd means)
The 2nd means of the present invention are as the large-scale phase-shift mask of the 1st means, and wherein, the both sides that are included in above-mentioned translucent phase shift region dispose the above-mentioned pattern that sees through region adjacently, and the width in above-mentioned translucent phase shift region is the width of the scope of 1 μ m to 5 μ m.
According to the 2nd means, in large-scale phase-shift mask, can prevent obvious side peak (side peak), and can prevent mask pattern exposure imaging being produced to recess during to photonasty resist on eurymeric resist surface, maybe the negative resist that should remove remains in the surface of substrate processing compared with unfertile land.
(the 3rd means)
The 3rd means of the present invention are as the large-scale phase-shift mask of any one in the 1st or 2 means, and wherein, above-mentioned translucent phase shift film is the individual layer that contains chromium and chromium compound or the structure of 2 layers.
According to the 3rd means, formed by chromium and chromium compound by translucent phase shift film, the pattern that can utilize Wet-type etching to carry out translucent phase shift film forms, and therefore, the effect of manufacturing cost that suppresses large-scale phase-shift mask is larger.
(the 4th means)
The 4th means of the present invention are as the large-scale phase-shift mask of any one in the 1st to 3 means, and wherein, the thickness of above-mentioned translucent phase shift film is the thickness of the scope of 0.1 μ m to 0.14 μ m.
According to the 4th means, see through the phase shift film of above-mentioned thickness by g ray, h ray, the i ray of extra-high-pressure mercury vapour lamp that makes the light source when exposing in the exposure device that utilizes large-scale mask to use at liquid crystal display, and make phase place with respect to the light reversion through seeing through region, thereby can obtain well the effect that makes the phase shift of the contrast raising of exposing patterns at imaging surface.
(the 5th means)
The 5th means of the present invention are as the large-scale phase-shift mask of any one in the 1st to 4 means, wherein, comprise the photomask being formed on above-mentioned transparency carrier, and translucent the 2nd translucent phase shift film forming to cover the mode of above-mentioned photomask, and comprise the mask pattern that disposes lightproof area and the 2nd translucent phase shift region, this lightproof area is stacked above-mentioned photomask and above-mentioned the 2nd translucent phase shift film of being provided with, the 2nd translucent phase shift region is arranged on above-mentioned lightproof area and above-mentionedly sees through between region and be only provided with above-mentioned the 2nd translucent phase shift film, and see through the phase place of exposure light in above-mentioned the 2nd translucent phase shift region with respect to seeing through the above-mentioned phase reversal of exposure light that sees through region.
According to the 5th means, by seeing through region, translucent phase shift region except comprising, also comprise the mask pattern that disposes lightproof area and the 2nd translucent phase shift region, the resist with various width that can expose well carries out patterning.
(the 6th means)
The 6th means of the present invention are manufacture methods of a kind of large-scale phase-shift mask, it comprises the following steps: prepare blank (blanks) with photonasty resist, to be that the one side at transparency carrier is stacked be coated with photonasty resist taking chromium and chromium compound to this blank with photonasty resist on the blank that the translucent phase shift film of material forms; And
Utilize describing device by the extremely above-mentioned blank with photonasty resist of required pattern exposure, after developing, carry out Wet-type etching, remove photonasty resist, and make above-mentioned translucent phase shift film form pattern.
According to the 6th means of the present invention, due to can 1 time the Wet-type etching pattern that carry out translucent phase shift film form, so it is larger to suppress the effect of manufacturing cost of large-scale phase-shift mask.
Invention effect
By using large-scale phase-shift mask of the present invention, can, in large-area region, improve translucent phase shift region and the contrast seeing through on the imaging surface in region to fine pattern.And then, owing to utilizing Wet-type etching to make phase shift film form pattern, so can reduce the manufacturing cost of large-scale phase-shift mask.
Brief description of the drawings
(a) of Fig. 1 is the sectional view of the structure of the large-scale phase-shift mask of explanation embodiments of the present invention.(b) be and (c) to represent the amplitude of exposure light of large-scale phase-shift mask of the present invention and the figure of the distribution of intensity.
(a) of Fig. 2 is the figure that the comparative example of the effect of phase-shift mask is described to (d).
Fig. 3 is the sectional view of the manufacturing step of explanation large-scale phase-shift mask of the present invention.
(a) of Fig. 4 is the variation that distributes of the exposure intensity while utilizing exposure emulation to obtain to make the situation that the width W in phase shift region changes and the curve that represented.(b) be the curve that amplifies the central portion of the exposure intensity distribution that represents (a).(c) be to represent the central light intensity of each exposure intensity distribution of (a) and the curve of the height at side peak.
Fig. 5 be exposure intensity to utilizing large-scale phase-shift mask of the present invention distribute, with the distribute curve of the exposure simulation result that compares gained of the exposure intensity of binary mask that utilizes identical patterns.
(a) of Fig. 6 is the planimetric map that represents embodiments of the present invention.(b) be the planimetric map that represents the binary mask of comparative example.(c) be the curve that represents overlappingly the exposure intensity distribution of embodiments of the present invention and the exposure intensity distribution of comparative example.
Fig. 7 schematically shows the sectional view of utilization as the situation of the intermediate tone mask replicated fine pattern of prior art.
(a) of Fig. 8 is the figure that the exposure intensity when situation of the intermediate tone mask exposure fine pattern that utilizes Fig. 7 is schematically described distributes, and (b) is the key diagram that the exposure intensity while schematically showing the situation of utilizing binary mask exposure fine pattern distributes to compare.
Fig. 9 is the key diagram that the example of the pattern to the translucent phase shift region in large-scale phase-shift mask of the present invention describes.
Figure 10 is another the routine skeleton diagram that represents large-scale phase-shift mask of the present invention.
Figure 11 is the key diagram that the phase shift region, edge in large-scale phase-shift mask of the present invention is described.
Figure 12 is the key diagram of the effect that promotes of contrast that the exposure intensity in the phase shift region, edge in large-scale phase-shift mask of the present invention is distributed and previous binary mask comparison.
Figure 13 is the routine general view that represents the large-scale phase-shift mask in reference example of the present invention.
Figure 14 is to the exposure intensity of the large-scale phase-shift mask in the reference example of the present invention figure describing that distributes.
Figure 15 is the enlarged drawing of the C part of Figure 14.
Figure 16 is the enlarged drawing of the D part of Figure 14.
Embodiment
Below, with reference to accompanying drawing, the structure to large-scale phase-shift mask of the present invention and the embodiment of manufacture method thereof describe.
Fig. 1 (a) is the sectional view that schematically shows the structure of an embodiment of large-scale phase-shift mask of the present invention.Fig. 1 (b) and Fig. 1 (c) are the figure that represents the effect under amplitude and the intensity of exposure light of the large-scale phase-shift mask of embodiments of the present invention.Fig. 2 (a)～(d) is the figure of the explanation width of pattern in translucent phase shift region and the comparative example of the relation of exposure intensity distribution shape.
(structure of large-scale phase-shift mask)
As shown in Fig. 1 (a), the structure of large-scale phase-shift mask 10 of the present invention is to comprise transparency carrier 1 and be formed on the translucent phase shift film 2 on above-mentioned transparency carrier 1, comprise and exposed seeing through region 3 and be only provided with the translucent phase shift region 4 of above-mentioned translucent phase shift film 2 on above-mentioned transparency carrier 1 of above-mentioned transparency carrier 1, and comprise the above-mentioned pattern that sees through region 3 and above-mentioned translucent phase shift region 4 adjacency, and the phase place of exposure light that sees through above-mentioned translucent phase shift region 4 is with respect to the phase reversal that sees through the above-mentioned exposure light that sees through region 3.Herein, so-called large-scale phase-shift mask refers to that at least its length is on one side mask more than 350mm.
(the exposure intensity distributed model of phase-shift mask)
Next, the model of the light intensity distributions on imaging surface (also referred to as " exposure intensity distribution ") of the exposure light that sees through large-scale phase-shift mask is described.Fig. 1 (b) represents the optical ampeitude on the imaging surface (particularly for photonasty resist face) of large-scale phase-shift mask, and Fig. 1 (c) represents that the exposure intensity on the imaging surface of large-scale phase-shift mask distributes.Light intensity is that the amplitude of light is carried out square and obtained, and the amplitude of light is followed its phase place and become positive and negative value, on the other hand, light intensity (identical with energy) only show on the occasion of.Again, exposure light 5 as Fig. 1 (a) as shown in as the direction irradiation of the translucent phase shift film 2 of self-induced transparency substrate 1 side direction.As exposure light 5, can be in the g of extra-high-pressure mercury vapour lamp ray (wavelength is 436nm), h ray (wavelength is 405nm), i ray (wavelength is 365nm), KrF excimer laser (wavelength is 248nm), ArF excimer laser (193nm) choice for use.With regard to practical aspect, because the pattern of tft array substrate is formed as large area, and the large light quantity of exposure light needs, so use the exposure light of 3 wavelength that only contain i ray, 2 wavelength that comprise h ray, i ray or comprise g ray, h ray, i ray.
Optical ampeitude when exposure light 5 is seen through to large-scale phase-shift mask 10, imaging surface imaging by the imaging optical system (not icon) of exposure device on resist is shown in the solid line 15 of Fig. 1 (b), light intensity distributions is shown in to the solid line 16 of Fig. 1 (c).As a comparative example, the light intensity distributions on the imaging surface when using photomask to replace the situation of translucent phase shift film 2 is shown in the dotted line 17 of Fig. 1 (c).
Exposure light 5 can be divided into the right side that sees through large-scale phase-shift mask 10 the light 11a that sees through region 3a, see through translucent phase shift region 4 light 11c, see through left side see through the light 11b of region 3b.There is following optical ampeitude shape,, the exposure light 11a that sees through large-scale phase-shift mask 10 is that transmittance is 100% the light that sees through seeing through in the 3a of region, and in the region except 3a (shading side), seeing through light is zero, exposure light 11b is that transmittance is 100% the light that sees through seeing through in the 3b of region, in the region except 3b, seeing through light is zero, and exposure light 11c is that transmittance is the light that sees through of T% in translucent phase shift region 4, beyond translucent phase shift region, seeing through light is zero.This exposure light 11a, 11b, 11c that is divided into 3 bundles is respectively by the imaging len (not shown) of exposure device, and forming 3 optical ampeitude shape 12a, 12b, 14 (in Fig. 1 (b), being represented by dotted lines) at imaging surface, the value that makes 3 optical ampeitude shapes be added gained becomes the optical ampeitude shape 15 (being called the principle of stack) of utilizing the imaging in exposure device of large-scale phase-shift mask 10.
On the other hand, if will see through except the optical ampeitude 14 of translucent phase shift region 4 and imaging, only obtain optical ampeitude 12a and 12b and, become and see through the optical ampeitude on imaging surface that translucent phase shift film 4 is replaced into the exposure light of the binary mask of photomask.
Making through the shape of optical ampeitude 12a of imaging surface of exposure light 11a imaging in exposure device that sees through region 3a is to form because of exposure light wavelength λ, the numerical aperture NA of imaging len and the aberration of the imaging len deviation of desirable imaging performance (from).The shape of the optical ampeitude 12a of imaging surface be projected to imaging surface to see through the border of region 3a be reference position, in the both sides on said reference position (border), reduce lentamente from seeing through the translucent phase shift of 3a side direction region, region 4 sides (quite in shading side), become after negative peak 13a once become negative light amplitude (being phase reversal), light amplitude moves closer in zero.Exceed light transmissive region as above border and shading side expansion be only called secondary lobe, in the distribution shape of secondary lobe, the part 13a that amplitude is become to maximum extreme value is called the peak value of secondary lobe.The position of peak value 13a of secondary lobe is relevant with the optical property of exposure device, and be formed on to the borderline phase of light transmissive region apart from proportional with exposure wavelength lambda, locate with the inversely proportional distance (i.e. proportional distance with λ/NA) of numerical aperture NA., the peak value of secondary lobe is formed in the distance that determines with the characteristic of the lens by exposure wavelength lambda and the exposure device position from the boundary position of the light transmissive region of photomask pattern.
Making through the shape of optical ampeitude 12b of imaging surface of the exposure light 11b imaging in exposure device that sees through region 3b is to make the shape left and right reversion of above-mentioned optical ampeitude 12a and the optical ampeitude shape being configured as reference position to see through the border in region 3b and translucent phase shift region 4, and has accordingly the peak value 13b of secondary lobe with the peak value 13a of secondary lobe.The light amplitude of the peak value 13b of secondary lobe and the peak value 13a of secondary lobe are similarly the negative value of phase reversal gained.
The shape that makes the optical ampeitude 14 of the exposure light 11c imaging surface of imaging in exposure device that sees through translucent phase shift region 4 and phase reversal is taking the border in translucent phase shift region as benchmark light amplitude reduces lentamente in its both sides, and becomes on the whole the optical ampeitude shape of the expansion with the mitriform of hanging of phase reversal.
See through the exposure light of large-scale phase-shift mask entirety by the imaging len of exposure device the optical ampeitude shape 15 of imaging surface imaging be utilize superposition law by optical ampeitude 12a, the 12b, 14 corresponding with 3 regions configure accordingly with the width W in translucent phase shift region 4, and addition obtain.Particularly, because the width W in translucent phase shift region 4 is also the border that sees through region 3a on right side, the distance on border that sees through region 3b with left side, so make and the seeing through optical ampeitude 12a on imaging surface corresponding to region 3a, be added (stack) with the distance W of the reference position that is separated by with 2 optical ampeitudes through the optical ampeitude 12b on imaging surface corresponding to region 3b in left side of right side, and then add the optical ampeitude 14 on the imaging surface corresponding with translucent phase shift region 4, and the light obtaining on imaging surface divides amplitude cloth 15.
(contrast lifting)
Light intensity distributions 16 on imaging surface shown in Fig. 1 (c) is that light amplitude 15 is carried out square and obtained.Therefore,, even if there is negative part in light amplitude, light intensity is just also being always.Light intensity distributions 17 is the light intensity distributions on the imaging surface while representing translucent phase shift region 4 to be replaced into the situation of lightproof area.Because the phase reversal of the light amplitude in translucent phase shift region 4 becomes negative value, so near the secondary lobe boundary portion of the light transmissive region in the light intensity distributions 16 on imaging surface is eliminated, compared with light intensity distributions 17 during with situation without translucent phase shift region 4, more emphasize dark portion, and the contrast of pattern is promoted.If because the width W of pattern is narrow, the light amplitude of secondary lobe strengthens, so must make the light amplitude grow of the phase reversal of its elimination, and must the transmittance T of translucent phase shift portion 4 be set highlyer.According to the effect in above-mentioned translucent phase shift region 4, the effect of dark portion of emphasizing light intensity distributions is shown in to the oblique line portion 18 of Fig. 1 (c).
(alleviating of side peak)
Next, the optical ampeitude 15 of the peak value of the width W on translucent phase-shifted region territory 4 and secondary lobe on imaging surface and the impact of light intensity distributions 16 describe.Secondary lobe is to produce because of the exposure wavelength of exposure device and imaging len, and the peak value (13a, 13b) of secondary lobe is created in the position with the boundary portion fixed distance of light transmissive region (3a, 3b).The phase reversal of the light amplitude of the peak value of this secondary lobe, sees through translucent phase shift region 4, mutually strengthens light amplitude with the exposure light 11c of phase reversal at imaging surface, and makes the region of point-like that exposure intensity is stronger or wire produce (being called side peak).This kind of side peak not forms the light intensity of the degree of pattern to resist at imaging surface, but make its sensitization in certain degree, in the time of the situation of eurymeric resist, in the time developing, the part on resist surface melts and formation recess, or in the time of the situation of negative resist, the resist that should remove is point-like or wire and remains in the surface of substrate processing compared with unfertile land.The recess on this kind of resist surface or resist remain in the photoresistance pattern inspection of semiconductor production step and are judged as defect, and become the obstacle of semiconductor production step.
The means A of the generation that alleviates side peak of the present invention is the mask that is made as following structure,, half width W that sees through phase-shifted region territory is restricted to below Wp, and the peak value 13a of the secondary lobe that sees through region 3a on right side, with the peak value 13b of the secondary lobe that sees through region 3b in left side can be not overlapped and grow.Particularly, the width W in translucent phase shift region is made as to the half width W p little width through phase-shifted region territory overlapping compared with the peak value of secondary lobe.Utilize afterwards Fig. 2 to describe the mask of this kind of structure.
Another means B of the generation that alleviates above-mentioned side peak of the present invention is the mask that is made as following structure,, make the width W in translucent phase shift region narrow, at above-mentioned translucent phase shift region central portion, the overlapping of positive amplitude part of secondary lobe increased, and eliminate the optical ampeitude 14 from the phase reversal in translucent phase shift region 4, thereby the light amplitude on imaging surface of the light that do not make to expose is for negative.The situation of the optical ampeitude on imaging surface of exposure light of the mask that utilizes this kind of structure is shown in to Fig. 1 (b).; make the more set width W q of the width W in translucent phase shift region 4 narrow; utilize the secondary lobe of optical ampeitude 12a and the secondary lobe of optical ampeitude 12b to offset to see through translucent phase shift region 4 and the phase place optical ampeitude 14 in imaging surface reversion, and the light amplitude 15 of the light that prevents from exposing becomes negative (phase reversal).If the light amplitude 15 of exposure light is just always, distribute in 16 at exposure intensity, can be along with light amplitude becomes zero and produce side peak.That is, can prevent following situation, that is, if light amplitude becomes zero, light intensity is also zero, and forms minimal value, attaches the peak value that forms light intensity in minimal value nearby.
On the other hand, the lower limit of width W is in the translucent phase shift region in region as being originally intended for use shading, increase with the light intensity that causes because of the overlapping increase of secondary lobe becomes the width Ws that the mode below set value limits, in the narrow pattern of wider width degree Ws, the exposure light that enters to dark portion increases, the pattern of resist forms insufficient, and cannot be used as photomask.
About the means A of impact that alleviates side peak, utilize Fig. 2 (a) as a comparative example～(d) base is described particularly in the variation of the light intensity distributions of the width W in translucent phase shift region and the peak of secondary lobe.Fig. 2 (a)～(b) is the comparative example that the peak value of secondary lobe is separated by, and Fig. 2 (c)～(d) is the overlapping comparative example of peak value of secondary lobe.The width W 2 that Fig. 2 (a) schematically shows translucent phase shift region is separated by compared with the peak value 13a of the secondary lobe that sees through region 3a on wide, right side, with the peak value 13b of the secondary lobe that sees through region 3b in left side and optical ampeitude that can interactional state.The peak value 13a of secondary lobe and the phase reversal of 13b and there is negative light amplitude, with see through the exposure light 24 in translucent phase shift region 4 and mutually strengthen at imaging surface, and in the optical ampeitude 25 of the exposure light of imaging surface, form peak value 21a, the 21b of obvious 2 phase reversals.
It is that optical ampeitude 25 is carried out square and obtained that the exposure intensity that comprises the mask in translucent phase shift region distributes, and its shape is schematically shown in to the curve 26 of Fig. 2 (b).The optical ampeitude 25 of exposure light along with to translucent phase shift region 4 near and reduce, after becoming zero, become negative peak 21a corresponding to the peak value 13a of secondary lobe.With the variation of this value accordingly, exposure intensity distributes 26 along with certainly leaning on and then reduce to translucent phase shift region 4 through region, become zero position at light amplitude, light intensity also becomes zero, next, and with on the occasion of increase, become negative peak 21a accordingly with light amplitude, light intensity becomes positive peak 29a (being called side peak), after this, and close to the light intensity corresponding with the transmittance T in translucent phase shift region 4.
Herein, because offside peak 29a adds the light amplitude that sees through light in phase shift region 4, so easily form recess or produce the residual problem of resist at substrate surface because binary mask causes on resist surface.
On the other hand, by translucent phase shift region 4, and the exposure intensity of pattern boundaries portion is distributed and improves steepness (contrast).The exposure intensity of binary mask is distributed and is shown in the dotted line 27 of Fig. 2 (b), distribute 26 difference of itself and the exposure intensity of mask that comprises translucent phase shift region is represented with oblique line portion 28.
According to schematically illustrating of above Fig. 2 (a), (b), judge in the time of the width W 2 abundant large situation in translucent phase shift region 4, compared with binary mask, contrast improves, but side peak is also higher.
Next, Fig. 2 (c), (d) represent with based on see through region 11a and 11b imaging surface light amplitude 12a secondary lobe peak value, select the comparative example of the width W in translucent phase shift region 4 with the overlapping mode of the peak value of the secondary lobe of light amplitude 12b.In Fig. 2 (c), represent the optical ampeitude on imaging surface 35 of the exposure light that utilizes the mask that comprises the translucent phase shift region 4 that width is Wp.The peak value 31 of optical ampeitude 35 is peak values of the not only secondary lobe that sees through region 3a on right side, overlapping with the peak value of secondary lobe that sees through region 3b in left side, and further adds the amplitude 34 of the light that sees through translucent phase shift region 4, and forms larger negative peak 31.
Fig. 2 (d) represents taking the peak value of the secondary lobe of light amplitude 12a, exposure intensity while selecting the situation of width W p in translucent phase shift region with the overlapping mode of the peak value of the secondary lobe of light amplitude 12b distributes 36 (as comparative example).The optical ampeitude 35 of exposure light reduces corresponding to translucent phase shift region 4, after becoming zero, becomes negative pole value at the peak value of secondary lobe.Corresponding to the variation of this optical ampeitude 35, exposure intensity distribute 36 along with certainly see through region before lightproof area so that reduce, become zero position at light amplitude, exposure intensity is also zero, next,, with on the occasion of increase, become negative peak accordingly with light amplitude, exposure intensity also becomes positive peak 39, is the light intensity distributions of symmetric figure afterwards.Herein, the peak value 39 of exposure intensity distribution 36 is to have 1 in central authorities, and make the peak value of 2 secondary lobes, be added and become larger peak value with the light transmission capacity in phase shift region 4, therefore, easily cause on resist surface and form recess or produce the residual problem of resist at substrate surface.
On the other hand, the distribution of the exposure intensity of pattern boundaries portion is the steepness (contrast) that improves light intensity distributions by translucent phase shift region.The exposure intensity of binary mask is distributed and is shown in the dotted line 37 of Fig. 2 (d), and itself and the difference of light intensity distributions 36 of imaging surface of the mask that comprises translucent phase shift region are represented with oblique line portion 38.
According to the explanation of above Fig. 2 (c), (d), when the situation of the overlapping width W p of the peak value that is secondary lobe in the width W in translucent phase shift region, compared with binary mask, contrast improves, but side peak is the highest.In the present invention, the width W p overlapping compared with the peak value of secondary lobe by the width W that makes phase shift region is narrow, and the impact at side peak is reduced.
According to the explanation that utilizes above the comparative example shown in explanation and Fig. 2 of effect of the present invention of Fig. 1, the present invention is by utilizing translucent phase shift film to form pattern, and the contrast that the exposure intensity of pattern boundaries portion is distributed promotes, simultaneously see through the overlapping width W p of the peak value of secondary lobe in region by the width W that makes translucent phase shift region narrow, and the generation that alleviates side peak.And then, by the mask that is made as following structure, and prevent the generation at side peak,, make the width W in translucent phase shift region narrow, the overlapping of positive amplitude part of secondary lobe increased, and eliminate the light amplitude from the phase reversal in translucent phase shift region 4, thereby the light amplitude on imaging surface of the light that makes to expose is for negative.
(structured material of large-scale phase-shift mask)
The concrete material that one side is faced each textural element of large-scale phase-shift mask 10 of the present invention with reference to the sectional view one of Fig. 1 (a) describes.The structure of the large-scale phase-shift mask 10 shown in Fig. 1 (a) is the photomasks that comprise transparency carrier 1 and be formed on the structure of the translucent phase shift film 2 on above-mentioned transparency carrier 1.
The transparency carrier 2 using in large-scale phase-shift mask 1 of the present invention is of a size of 350mm × 350mm to 1220mm × 1400mm, and thickness is 8mm～13mm.Material can be used low-expansion glass (aluminium borosilicate glass, pyrex), the synthetic quartz glass through optical grinding, is preferably and uses the synthetic quartz glass that coefficient of thermal expansion is less and ultraviolet transmittance is higher.
(structure of translucent phase shift film)
The structure of translucent phase shift film 2 has following 2 kinds of forms, that is, selection can make the to expose thickness of phase reversal of light obtains the material of required light transmittance and forms with monofilm; And be made as the transmittance that contains the material that the transmittance that mainly makes the phase place adjustment layer of the material that the transmittance of phase reversal is higher and contain major decision transmittance is lower and adjust the structure of 2 layers of layer.
In the time forming the situation of translucent phase shift film 2 with individual layer, selective refraction rate n higher (being generally more than 1.5) and can to make wavelength be the material that the thickness d (d=λ/2 (n-1)) of the phase reversal of the exposure light of λ obtains required transmittance in 4% to 30% scope.The material of the translucent phase shift film forming with individual layer as this kind, can illustrate nitrogen chromium oxide (CrON), nitrogen molybdenum silicide (MoSiN), silicon oxynitride molybdenum (MoSiON), silicon oxynitride (SiON), titanium oxynitrides (TiON), and change the containing ratio of oxygen or nitrogen and adjust transmittance.
In the time of the situation with 2 layers of translucent phase shift film 2 of formation, first, adjust the material of layer as phase place, be chosen in also higher material of the higher and light transmittance of refractive index under exposure wavelength, and be made as the layer that makes phase reversal, and then, adjust the material of layer as transmittance, be chosen in the lower material of transmittance under exposure wavelength, as the film entirety of 2 layers, adjust each thickness so that the phase reversal of exposure light and transmittance become the mode of required value.Adjust the material of layer as phase place, use nitrogen chromium oxide (CrON), fluorine chromium oxide (CrFO), silicon oxynitride (SiON), silicon oxynitride molybdenum (MoSiON), titanium oxynitrides (TiON), adjust layer as transmittance, use chromium (Cr), chromium nitride (CrN), tantalum (Ta), titanium (Ti).Phase place adjustment layer is made as to nitrogen chromium oxide (CrON) and transmittance adjustment layer is made as to the combination of chromium nitride (CrN), phase place adjustment layer is made as to fluorine chromium oxide (CrFO) and transmittance adjustment layer is made as to the combination of chromium nitride (CrN) and phase place adjustment layer is made as to silicon oxynitride molybdenum (MoSiON) and transmittance adjustment layer is made as to the combination of the silicon oxynitride molybdenum (MoSiON) that oxygen ratio is less compared with phase place adjustment layer as forming the concrete combination of materials of translucent phase shift films with 2 layers, can illustrating.
The individual layer of the oxides of nitrogen of the oxide that contains chromium and chromium if especially translucent phase shift film 2 is made as, the nitride of chromium, chromium or the structure of 2 layers, in the time that pattern forms, can utilize the cerous nitrate with good pattern processability is that wet etchant is carried out Wet-type etching, and the advantage in manufacturing cost is larger.Especially for the phase shift film of 2 layers of structure, can utilize cerous nitrate is that wet etchant is carried out Wet-type etching to 2 kinds of layers in a step, and can shorten step.Particularly, as the translucent phase shift film of individual layer, can illustrate nitrogen chromium oxide (CrON) film of individual layer.As the translucent phase shift film of 2 layers, can illustrate the translucent phase shift film that phase place adjustment layer is made as to nitrogen chromium oxide (CrON) and transmittance adjustment layer is made as to the combination of chromium nitride (CrN) again.
Moreover translucent phase shift film also can arrange low reflection layer if necessary in surface, and surperficial reflected light is reduced.As the material of low reflection layer, can use chromium oxide (CrO).
The required optical characteristics of translucent phase shift film 2 using in the present invention is described.That obtains translucent phase shift film 2 makes to expose the thickness of phase reversal of light 5, between the phase difference producing by phase shift film at the refractive index n of the thickness d of phase shift film, phase shift film, exposure light wavelength λ, with the light that exposes, there is the relation of φ=2 π (n-1) d/ λ, because phase differential reversion is φ=π, so the thickness d of phase differential reversion becomes λ/2 (n-1).Particularly, if exposure light wavelength lambda is the 365nm of i ray, the refractive index n of phase shift film is 2.55, and the thickness that can calculate phase shift film is 118nm.The scope of 10 left and right that the permissible range of the variation of the thickness of phase shift film is is positive and negative percentage with respect to the thickness of the phase shift film calculating, if in this permissible range, phase-shift mask can obtain the effect of sufficient phase shift.
In the time that the light that exposes as extra-high-pressure mercury vapour lamp comprises the situation of a plurality of peak wavelengths (having 3 bright-line spectrums), calculate the thickness of the phase shift film to each peak wavelength, utilize thickness ratio weighting gained and (being called weighted mean) decision phase shift film of the energy intensity of the exposure light to divide into each peak wavelength.For example, in the time using g ray to there is Pg, h ray to have the light source of energy intensity that Ph, i ray have a Pi as the situation of exposure light source, if the thickness of the phase shift film corresponding with g ray is Dg respectively, the thickness of the phase shift film corresponding with h ray is Dh, the thickness of the phase shift film corresponding with i ray is Di, and utilizing the thickness D of the phase shift film that weighted mean obtains is D=(Pg × Dg+Ph × Dh+Pi × Di) ÷ (Pg+Ph+Pi).Particularly, if Pg=2, Dg=141nm, Ph=1, Dh=130, Pi=3, Di=118nm, utilizing the thickness D of the phase shift film that weighted mean obtains is 128nm.By using this kind to utilize the thickness D of the phase shift film that weighted mean obtains, even if be the exposure light that comprises a plurality of peak wavelengths, also can obtain well the effect of phase-shift mask.
Obtain the method for the thickness D of phase shift film as utilizing weighted mean, also the value of sensitivity gained that the energy intensity of the exposure light to each peak wavelength is multiplied by the resist of corresponding wavelength can be applied as the method for average weighted weight, better result can be obtained.
The light transmittance of translucent phase shift film 2 is the values that are set as uprising through the contrast of pattern of exposure.Particularly, the light transmittance under the exposure light of phase shift film 2 is preferably more than 4% and below 30%.If the transmittance of translucent phase shift film is below 4%, utilize the effect of phase shift raising contrast less.If the width W of translucent phase shift film is narrow, because causing the contrast of pattern, reduces secondary lobe light, therefore, the transmittance in translucent phase shift region is set highlyer, if but more than 30%, light shielding ability reduces, so impracticable.
In the time that large-scale phase-shift mask of the present invention comprises the situation of following the 2nd translucent phase shift film, the light transmittance that is more preferred from translucent phase shift film is more than 4% and below 15%.Its reason is: because the light transmittance of the 2nd translucent phase shift film is preferably the above-mentioned scope that is made as, so can form translucent phase shift film and the 2nd translucent phase shift film simultaneously, and can be made as the large-scale phase shift film that productivity is higher.
As the pattern form in translucent phase shift region, can suitably select according to the purposes of large-scale phase-shift mask etc.As the pattern form in this kind of translucent phase shift region, for example, can enumerate in following Fig. 6 (a) illustrative translucent phase shift region 4 in illustrative L & S pattern form, Fig. 9 and in transparent region 3, be configured to dot pattern shape of island etc.
L & S pattern form for example can be preferably as in order to form the signal electrode such as gate electrode, source drain electrode, distribution electrode or to be formed on the pattern form of the transparency electrode etc. of the fine rule on opposed base material.
Dot pattern shape for example can be preferably as hole pattern form in the time forming contact hole in tft array substrate etc.
In the present invention, as the pattern form in translucent phase shift region, be wherein preferably the transparency electrode pattern form of pattern form for hole, fine rule.
Moreover Fig. 9 is the key diagram that the example of the pattern to the translucent phase shift region in large-scale phase-shift mask of the present invention describes.
As the width in translucent phase shift region, can suitably select according to the purposes of large-scale phase-shift mask etc., be preferably in the scope of 1 μ m～5 μ m, be wherein preferably in the scope of 1.0 μ m～3.0 μ m, You Jia is in the scope of 1.5 μ m～2.5 μ m.
Be in above-mentioned scope by above-mentioned width, and in large-scale phase-shift mask of the present invention, can prevent the generation at obvious side peak.
The width in the translucent phase shift region in so-called the present invention refers to the distance representing with W in Fig. 1 (a), Fig. 5 (a), Fig. 6 (a), Fig. 9.
Herein, as an example of eurymeric resist example, the impact on resist causing because of side peak is described.As mentioned above, side peak is mutually to strengthen at imaging surface the region that light amplitude produces with the exposure light that sees through translucent phase shift region because of the peak value of secondary lobe.Again, side peak is normally created in the region in translucent phase shift region, and is compared with seeing through the light intensity of exposure light in translucent phase shift region, the region of its light intensity grow.
Therefore, in the time using eurymeric resist for example as the situation of resist, at the side peak being created in translucent phase shift region, because the exposure of resist is carried out, so there is resist surface after exposure to produce the problem of recess.Can bring into play the function of protection lower floor though there is the resist of above-mentioned recess, in the inspection of carrying out, have the situation of the defect of being detected as after the development step of resist.Thus, because the resist originally with defencive function is also because inspection is identified as defective, causes and cannot use, so the problem that has the productivity of tft array substrate etc. to reduce.
With respect to this, because of in the time that the width in translucent phase shift region is made as to the situation in above-mentioned scope, can suppress the generation at side peak, so the resist surface that can be suppressed at after exposure produces recess.Thus, by using large-scale phase-shift mask of the present invention, can make TFT substrate etc. for productivity the higher person.
Again, about the impact on resist causing because of side peak, in the time using the situation of negative resist, the for example side peak in translucent phase shift region, the exposure of resist is carried out, and after exposure, resist can be remaining, therefore, in the inspection of carrying out, there is the situation of the defect of being detected as after the development step at resist.There is the situation that is difficult to carry out well etching of the lower floor after above-mentioned exposure etc. again.
With respect to this, because of in the time that the width in translucent phase shift region is made as to the situation in above-mentioned scope, can prevent the generation at side peak, so can suppress resist remaining after exposure.
According to above content, large-scale phase-shift mask of the present invention can preferably use in the TFT of display device substrate etc. in the time of the structure as forming the above-mentioned width that becomes translucent phase shift region.
As long as large-scale phase-shift mask of the present invention comprises above-mentioned region and the translucent phase shift region of seeing through, be not particularly limited, also can optionally there is the structure except above-mentioned.
As this kind of structure, for example, as Figure 10 (a), (b) shown in, comprise the photomask 101 being formed on transparency carrier 1, and translucent the 2nd translucent phase shift film 102 forming to cover the mode of photomask 101, can enumerate that to dispose the mask pattern in lightproof area 103 and the 2nd translucent phase shift region 104 (following, have this mask pattern is called to the situation that phase shift region, edge describes), stacked photomask 101 and the 2nd translucent phase shift film 102 of being provided with of this lightproof area 103, the 2nd translucent phase shift region 104 is arranged on lightproof area 103 and sees through between region 3, and be only provided with the 2nd translucent phase shift film 102.The 2nd phase shift region 104 in phase shift region, edge, sees through the phase place of exposure light in the 2nd translucent phase shift region 104 with respect to the phase reversal of exposure light through seeing through region 3.
Figure 10 (a) is another the routine general view that represents large-scale phase-shift mask of the present invention, and Figure 10 (b) is the AA line sectional view of Figure 10 (a).Again, in Figure 10 (a), for being easy to explanation, and with the region representation lightproof area by dotted line.
As mentioned above, when the situation of phase-shift mask of the present invention in the width in translucent phase shift region is the scope of above-mentioned 1 μ m～5 μ m, less because of the impact that side peak causes, can well resist be exposed.Thus, be preferably above-mentioned translucent phase shift region in order to the photoresistance patterning of the width in the scope of above-mentioned 1 μ m～5 μ m will be there is.
On the other hand, conventionally, TFT substrate etc. comprises the structure with various width, during fabrication, is preferably simultaneously photoresistance film is exposed, and will have the photoresistance patterning of various width.Therefore, 2 regions that only comprise the translucent phase shift region that sees through region and have various width at phase-shift mask are during as the situation of mask pattern, and the kind of worry conditions of exposure or the resist that uses etc. are more restricted.
For above-mentioned worry, can consider in phase-shift mask of the present invention, further setting only comprises the lightproof area that is formed on the photomask on transparency carrier.
But the requirement of the high-precision refinement of pattern in recent years uprises, and there is the situation that cannot ignore the impact of resist causing because of exposure diffraction of light.As the impact on above-mentioned resist, particularly, can enumerate due to because exposure diffraction of light produces secondary lobe on the border that sees through region and lightproof area, so the end face of resist does not have required steepness, and be difficult to make the contrast of mask pattern abundant.
On the other hand, in the time that phase-shift mask of the present invention comprises the situation in phase shift region, above-mentioned edge, due to following reason, and can make the end face of resist be more precipitous shape,, the contrast of the pattern of resist is promoted.
Figure 11 is the key diagram that the phase shift region, edge in the present invention is described, exposure light 5 is seen through to the seeing through region 3 of large-scale phase-shift mask 1 and optical ampeitude when imaging surface imaging on resist is shown in the dotted line 110 of Figure 11 (b), light intensity distributions is shown in to the dotted line 113 of Figure 11 (c).If without exposure diffraction of light, optical ampeitude should become rectangular-shapedly at imaging surface, but becomes the optical ampeitude of the expansion with the mitriform of hanging because of the diffraction of exposure device (not icon) etc.On the other hand, see through the phase reversal of the exposure light 5 in the 2nd translucent phase shift region 104 of Figure 11 (a), and become negative optical ampeitude as shown in the dotted line 111 of Figure 11 (b).By as offset by this kind of negative optical ampeitude 111, with the light amplitude of expansion of optical ampeitude 110 that sees through region 3 as position configuration the 2nd translucent phase shift region 104 and add phase shifted light and the distribution of amplitudes of the light of the distribution of amplitudes expansion of the light that prevents from exposing is shown in the solid line 112 of Figure 11 (b).The light intensity that comprises the phase shifted light corresponding with the distribution of amplitudes 112 of light that is added with phase shifted light is distributed and is shown in the solid line 114 of Figure 11 (c) again.If only relatively see through the light intensity distributions 113 in region, distribute 114 with the light intensity that comprises phase shifted light, with the position in the 2nd translucent phase shift region 104 accordingly, light intensity reduces, and suppresses the expansion of light intensity.The part that this light intensity is reduced represents with oblique line portion 115.On the other hand, the outside reducing in light intensity, observes the light intensity part of grow (Figure 11 (c) 116) again that is called side peak (following, to have the situation that is called the side peak in phase shift region, edge).Above-mentioned side peak is grow in the time that the transmittance that makes the 2nd translucent phase shift region improves, but must suppress for the photostable level of resist.
Below, the details in the phase shift region, edge in the present invention is described.
The pattern form in phase shift region, above-mentioned edge is suitably to select according to the purposes of large-scale phase-shift mask etc.In the present invention, be preferably the pattern form that there is width that the pattern form in more above-mentioned translucent phase shift region is large, is greater than the width of 5 μ m.About the pattern form in phase shift region, above-mentioned edge, particularly, can enumerate line pattern shape, L & S pattern form, some shape etc.
The width of the lightproof area in phase shift region, above-mentioned edge can suitably be selected according to the purposes of phase-shift mask of the present invention etc.
As the width in the 2nd translucent phase shift region in the present invention, as long as can suppress the expansion of the light intensity that sees through region, and can be by resist exposure for required pattern form, just be not particularly limited.
As the width in this kind the 2nd translucent phase shift region, be preferably below 3.5 μ m, wherein, be preferably below 2.5 μ m, You Jia is below 2.0 μ m.Its reason is: in the time that the width in above-mentioned the 2nd translucent phase shift region exceedes the situation of above-mentioned value, depart from the scope that the effect of phase shift relates to, and the possibility that the effect that has the contrast that makes exposing patterns to strengthen reaches capacity.Again, its reason is: in the 2nd translucent phase shift region seeing through between region and lightproof area, the impact of the peak value (the side peak in phase shift region, edge) of the light intensity distributions of residual optical ampeitude is not larger with seeing through that the light amplitude in region offsets, resist produces reaction to the light that sees through that sees through the 2nd translucent phase shift region, and in the pattern form of resist, produce recess etc., and in distress so that the possibility that the pattern form of resist is required form.
Again, in the present invention, due to can be by comprising the 2nd translucent phase shift region, and suppress to see through the expansion of the light intensity in region, so about the lower limit of the width in the 2nd translucent phase shift region, as long as for forming the degree of translucent phase shift film, just be not particularly limited, more than being preferably 0.25 μ m, wherein, more than being preferably 0.5 μ m, You Jia is more than 0.8 μ m.Its reason is the 2nd translucent phase shift region to be set good alignment precision.Again, its reason is: in the time of the situation less than above-mentioned value, the light quantity of phase reversal reduces, and the less possibility that produces effect.
Again, when the width b in above-mentioned the 2nd translucent phase shift region is the scope more than 0.5 μ m and below 2 μ m, the effect of phase shift is the most obvious.
Herein, the width b in the 2nd translucent phase shift region measures the bee-line from the distance gained through region and the translucent phase shift region, border to the 2 in the 2nd translucent phase shift region and the border of lightproof area abreast with transparency carrier surface.Again, in Figure 11 (a), its distance for representing with b.
Again, as shown in Figure 12 (a), while comprising the situation that sees through region 3 between the 2nd translucent phase shift region 104 at phase-shift mask of the present invention in phase shift region, the edge of adjacency, as the above-mentioned width a that sees through region 3, more than being preferably 1 μ m and below 6 μ m.Herein, the resolution pole of large-scale projection type exposure device is limited to 3 about μ m, and the problem of large-scale phase-shift mask of the present invention is the above-mentioned resolution limit (contrast of drawing pattern improve exposing patterns of 3 μ under m).
When seeing through the width a in region 3 because above-mentioned and being greater than the situation of 6 μ m, because of the impact that the resolution limit of exposure device produces less, so the DeGrain of large-scale phase-shift mask of the present invention.In the time that the above-mentioned width a that sees through region 3 is less than the situation of 1 μ m, even if add the effect of phase shift of the present invention, also cannot separate picture to exposing patterns again.Herein, the width a that sees through region 3 is the diameter that becomes the maximum inscribed circle that sees through region shape of the object in transparency carrier plane, if object sees through the rectangle that is shaped as in region, the length of minor face is the width that sees through region.
Herein, the resolution limit of above-mentioned large-scale projection type exposure device is in the time of the situation that uses binary mask to expose in above-mentioned large-scale projection type exposure device, can regard as comparably and the minimum value (following, to have the situation of the width that is called resolution limit) of the width that sees through region of binary mask that can stably separate picture in exposure area.
Phase-shift mask of the present invention, in the time of the situation using in the lump with large-scale projection type exposure device, can be separated picture to the pattern of drawing below the width of the resolution limit of above-mentioned binary mask.
As the width of drawing pattern of phase-shift mask of the present invention, being preferably with respect to the width of the resolution limit of the binary mask in large-scale projection type exposure device is below 100%, wherein be preferably below 85%, and be preferably more than 30%, be wherein preferably more than 40%.Its reason is: during less than the situation of above-mentioned scope, have the possibility that is difficult to separate drawing pattern itself picture at the above-mentioned width of drawing pattern.Again, its reason is: in the time that the above-mentioned width of drawing pattern exceedes the situation of above-mentioned scope, have the possibility that is difficult to give full play to the effect of utilizing phase shift.When the equal situation of the width of drawing pattern in above-mentioned phase-shift mask and the width of resolution limit, compared with the situation of utilizing binary mask to expose, can make the shape of resist good.
The above-mentioned width of drawing pattern can be based on the intrinsic width of resolution limit of large-scale projection type exposure device and the sensitivity of resist, determines by adjusting the seeing through the width in region and width, the transmittance of translucent phase shift film etc. in the 2nd translucent phase shift region of phase-shift mask of the present invention.
Herein, as shown in Figure 12 (b), the width that sees through region of binary mask is to measure abreast certainly and see through the bee-line of the distance gained on a border to another border of the lightproof area of region adjacency with one with transparency carrier surface, and is the distance representing with d.
Again, the width of drawing pattern of so-called phase-shift mask refers to utilize and sees through region and the 2nd translucent phase shift region and draw to the width of the pattern on resist.
Next, the photomask for phase shift region, edge and the 2nd translucent phase shift film are described.
As the photomask for lightproof area, need to be below 0.1% and the material of easily carrying out pattern processing at transmittance under exposure wavelength.As the material of this kind of photomask, can use chromium, chromium compound, molybdenum silicides, tantalum compound, be preferably use and can utilize Wet-type etching to carry out good pattern to form and use the also more photomask taking chromium or chromium compound as major component of actual achievement.Use and hide the thinner chromium nitride getting final product of optical activity thickness higher and photomask as chromium compound.If the relatively photomask of chromium and the photomask of chromium nitride, use has the mask blank of easy film forming and the higher chromium photomask of versatility easily to obtain, so better.Particularly, in the time that the film of crome metal is made as to the situation of photomask, for the transmittance of the light that makes to expose is below 0.1%, be the above person of 70nm and use thickness.On the other hand, if make thickness thicker, etching period increases, and processability reduces, and therefore, conventionally under the thickness below 150nm, uses.
The width of lightproof area can suitably be selected according to the purposes of phase-shift mask of the present invention etc.
Next, the 2nd translucent phase shift film for phase shift region, edge is described.
The 2nd translucent phase shift film is to cover the side of above-mentioned photomask and the mode of upper surface is formed on transparency carrier.
The transmittance of the 2nd translucent phase shift film is the value not being set as in the scope at edge phase shift region generating side peak utilizing the effect of phase shift as uprising through the contrast of pattern of exposure.Particularly, the light transmittance under the exposure light of the 2nd translucent phase shift film is preferably more than 4% and below 15%.If the transmittance of the 2nd translucent phase shift film is below 4%, utilize the effect of phase shift raising contrast less, if the transmittance of phase shift film is more than 15%, the effect of phase shift is crossed strong and is caused submaximum in lightproof area (the side peak in phase shift region, edge) to uprise, thereby produces the possibility that becomes defect.
Because the thickness of the 2nd translucent phase shift film, material can be identical with the thickness of above-mentioned translucent phase shift film, material, so omit explanation herein.In the present invention, be preferably above-mentioned translucent phase shift film identical with thickness, the material of the 2nd translucent phase shift film.Its reason is to form translucent phase shift film and the 2nd translucent phase shift film simultaneously.
In the present invention, by selecting chromium or chromium nitride as photomask, selective oxidation chromium (CrO) or nitrogen chromium oxide (CrON) are as the 2nd translucent phase shift film, can same etching machines be processed by photomask and the 2nd translucent phase shift film, and can to utilize the cerous nitrate with good pattern processability be wet etchant that both of photomask and the 2nd translucent phase shift film are carried out to Wet-type etching, the advantage on cost is larger.Again, in the present invention, due to by the 2nd translucent phase shift film to cover the side of above-mentioned photomask and the mode of upper surface is formed on transparency carrier, so in the time carrying out Wet-type etching, can suppress the photomask of etching lower floor.
As long as the phase shift region, edge in the present invention comprises above-mentioned photomask and the 2nd translucent phase shift film, just be not particularly limited, in addition, also can suitably select and append required structure again.As this kind of structure, can enumerate anti-reflective film.
, in common large-scale projection type exposure device, be difficult to only irradiate directional light as exposure light herein, mostly be the situation that comprises the light with set angle in a part for exposure light.And then, penetrate as parasitic light at the reflected light on the light of pattern edge diffraction and invagination or the border of film etc.Again, this kind of parasitic light is due to the irradiation position in large-scale projection type exposure device, different from the position that in fact arrives resist, so there is the worry of the also exposure resist corresponding with the lightproof area that did not originally need the phase-shift mask exposing.
Again, in the present invention, lightproof area has the structure that is laminated with photomask and is laminated with the 2nd translucent phase shift film on transparency carrier on photomask.Again, the 2nd translucent phase shift film has the thickness D that phase differential is π.Therefore, for example, in the time using phase-shift mask of the present invention by the situation of the photoresistance patterning in order to make tft array substrate etc., can think the following behavior of above-mentioned parasitic light performance.First, the parasitic light irradiating from large-scale projection type exposure device sees through the transparency carrier of phase-shift mask, becomes reflected light through reflections such as the metal electrodes of tft array substrate.Next, the reflected light of above-mentioned parasitic light is incident to the 2nd translucent phase shift film of lightproof area, becomes the 2nd reflected light through photomask reflection, and again from the 2nd translucent phase shift film outgoing.Thus, be incident to the reflected light of the parasitic light of the 2nd translucent phase shift film of above-mentioned lightproof area, be 2 π through photomask reflection from the 2nd catoptrical phase differential of the parasitic light of the 2nd translucent phase shift film outgoing.Therefore, due to the surface at the 2nd translucent phase shift film, above-mentioned reflected light and above-mentioned the 2nd reflected light strengthen mutually, so there is the impact on resist causing because of parasitic light more obviously to worry.
The problems referred to above are the problems that produce because of the layer structure of the lightproof area in the present invention.
In the present invention, with regard to the viewpoint of the parasitic light countermeasure in when exposure, comparatively it is desirable to lightproof area and there is anti-reflection function.As shown in Figure 11 (a), the lightproof area 103 using in the present invention has the structure that is laminated with photomask 101 and is laminated with the 2nd translucent phase shift film 102 on transparency carrier 1 on photomask 101, but because the 2nd translucent phase shift film 102 has the thickness D that phase differential is π, so by the exposure light (the 2nd reflected light of parasitic light) of surface reflection of photomask 101 and the phase differential of the surperficial reflected light (reflected light of parasitic light) of the 2nd translucent phase shift film 102 be 2 π and mutually strengthen.For alleviating this impact, the anti-reflective film 105 that comprises semi-transparent film also can be set between photomask and the 2nd translucent phase shift film.By comprising anti-reflective film 105, the mode that can mutually weaken by the light that light and anti-reflective film were reflected so that photomask the was reflected reflected light of the parasitic light on anti-reflective film surface (light (the 2nd reflected light of parasitic light) that photomask was reflected with) is set optical path length, prevents that phase differential from becoming 2 π and mutually strengthens.
As the anti-reflective film in the present invention, as long as there is anti-reflection function, and can be formed between the photomask and the 2nd translucent phase shift film of lightproof area, just be not particularly limited, can preferably use metal film, metallic compound film etc.
As the material of above-mentioned anti-reflective film, chromium oxide (CrO), nitrogen chromium oxide (CrON), chromium nitride (CrN), titanium dioxide (TiO), tantalum oxide (TaO), nickel oxide aluminium (NiAlO) etc. be can enumerate, chromium oxide (CrO), nitrogen chromium oxide (CrON) wherein can be preferably used.
The thickness of above-mentioned anti-reflective film is to become the mode of the optical path length that light that light that photomask reflects and anti-reflective film reflect weakens is mutually designed.
As the thickness of this kind of anti-reflective film, be preferably the light transmission anti-reflective film reflecting by photomask, and the phase differential that makes the light that light that photomask reflects and anti-reflective film reflect becomes the thickness in the scope of π ± 10, wherein, be preferably the thickness in the scope that becomes π ± 5, You Jiawei becomes the thickness of π.
Its reason is to make the light that light that photomask reflects and anti-reflective film reflect preferably to weaken, and can preferably prevent because of parasitic light produce abnormal.
The concrete thickness of above-mentioned anti-reflective film is suitably to select according to the material of anti-reflective film etc., is not particularly limited, and is preferably in the scope of 0.01 μ m～0.1 μ m, wherein, is preferably in the scope of 0.02 μ m～0.05 μ m.Its reason is: in the time of the situation less than above-mentioned scope, there is the possibility that is difficult for forming with uniform thickness anti-reflective film, and its reason is: in the time exceeding the situation of above-mentioned scope, and the possibility that exists film formation time, the cost of anti-reflective film to spend morely.
As anti-reflective film, except using the phase place person who adjusts the light that sees through, for example, also can use roughened the surface of metal film etc. and give the merit able one who makes light diffusion again.
As the surperficial antireflection method of the 2nd translucent phase shift film, also can translucent low-reflection film be set on the surface of the 2nd translucent phase shift film.Especially in the time that the 2nd translucent phase shift film is the situation of nitrogen chromium oxide, have the situation on surface with metallic luster, in the time of this situation, the low reflection layer that contains chromium oxide is comparatively effective.
In large-scale phase-shift mask of the present invention, in the time comprising the situation in phase shift region, above-mentioned edge, the resist of use is preferably the less person of impact who is subject to the side peak in phase shift region, above-mentioned edge.As mentioned above, in the present invention, translucent phase shift region is due to can be by the width being made as in the scope of 1 μ m～5 μ m, and makes side peak be difficult for producing, so by using the resist of selecting in the above described manner, shape that can be better is by photoresistance patterning.
As the purposes that only comprises the large-scale phase-shift mask in above-mentioned the present invention who sees through region and phase shift region, can enumerate in order to by the large-scale phase-shift mask of the fabrication patterning of explanation in the item of the pattern form in above-mentioned phase shift region.
Again, the purposes of the large-scale phase-shift mask while comprising the situation in phase shift region, above-mentioned edge is not particularly limited, and is preferably to utilize translucent phase shift region by photoresistance patterning less width, utilizes phase shift region, edge by photoresistance patterning larger width.For example, as shown in above-mentioned Figure 10 (a), (b), can enumerate: in order to the photoresistance patterning that utilizes translucent phase shift region 4 that the transparency electrode of fine rule is used, utilize the large-scale phase-shift mask of the photoresistance patterning that phase shift region, edge uses gate electrode or source drain electrode; Though or not shown, in order to the photoresistance patterning that utilizes translucent phase shift region that contact hole is used, utilize large-scale phase-shift mask of the photoresistance patterning that phase shift region, edge uses above-mentioned gate electrode or source drain electrode etc., but be not limited to these.
(manufacture method)
Fig. 3 is the sectional view that represents the manufacturing step of large-scale phase-shift mask of the present invention.
For making the large-scale phase-shift mask 1 of present embodiment, first, prepare to be laminated with the photomask blank 41 (Fig. 3 (a)) of translucent phase shift film 2 on transparency carrier 1.The synthetic quartz through optical grinding that the common used thickness of transparency carrier 1 is 8mm～12mm.If the translucent phase shift film of photomask blank 41 2 individual layers of nitrogen chromium oxide layer or the transmittance of chromium nitride are adjusted two layers of phase shift film of layer and nitrogen chromium oxide, utilize sputtering method film forming.
Next, by the translucent phase shift film 2 of above-mentioned photomask blank 41 according to usual way patterning., on translucent phase shift film 2, the coating photonasty resist corresponding with the exposure wavelength of laser beam describing device toasts given time after coating, forms the photoresistance film of even thickness.Next, utilize laser scanning picture device to draw required pattern to photoresistance film, and develop, and form resist 42 (Fig. 3 (b)).Conventionally, Wiring pattern or contact hole pattern, gate pattern etc. that the TFT transistor that translucent phase shift region 4 is display panels is used, optionally form the mark that position alignment uses and used.
Next, etching is also removed the translucent phase shift film exposing from resist 42, remaining resist is peeled off and removed, and obtain the transparency carrier 1 (Fig. 3 (c)) that is formed as the translucent phase shift film of the shape in translucent phase shift region 4 with pattern.The etching of translucent phase shift film 2 can be applied wet etching or dry etching method, but due to the maximization along with the photomask using in flat-panel monitor as mentioned above, and in dry-etching, the maximization of Etaching device spends huge cost, also be difficult to control the etched homogeneity in large area simultaneously, so with regard to cost aspect, be preferably Wet-type etching.If translucent phase shift film 2 is the film that comprises chromium based material, can be used in the wet etchant that was added with chloric acid in ammonium ceric nitrate and carries out well pattern formation.
Manufacturing method according to the invention, because the pattern that can utilize the Wet-type etching of 1 step to carry out translucent phase shift film forms, so it is larger to suppress the effect of manufacturing cost of large-scale phase-shift mask.
In the time that manufacture comprises the situation of phase-shift mask in phase place region, above-mentioned edge, can be by the 2nd photomask blank that is used in basic unit on transparent base and has photomask and be optionally laminated with anti-reflective film, photomask etc. is etched to after set pattern, translucent phase shift film is formed on to whole of the surface of the side such as photomask of transparency carrier, and prepares photomask blank.
In the time of the translucent phase shift film of etching, be etched into the pattern in translucent phase shift region and the 2nd translucent phase shift region again.
Owing to making, formation method and the engraving method of photomask and anti-reflective film are identical with translucent phase shift film, so omit explanation herein.
(other)
Phase-shift mask of the present invention is the photoresistance patterning in order to the pattern for above-mentioned tft array substrate etc. is formed.
Can suitably select according to the electrode material of TFT substrate, developer solution, projection type exposure machine etc. with the resist that phase-shift mask of the present invention uses in the lump, be not particularly limited.
For example using the exposure machine of Nikon (Nikon) company system as exposure machine, use AZ1500 as resist, while using AZ300MIF as developer solution, be that the impact of exposure light of the part below 5% is less, to be difficult to utilize exposure intensity be that light below 5% is drawn resist owing to can making the transmittance of phase-shift mask, so the side peak being difficult for during exposure intensity is distributed produces reaction, and can carry out well the patterning of resist.
Again, the thickness of resist, as long as for can utilize phase-shift mask of the present invention to be patterned as the degree of required shape, is just not particularly limited, and is preferably in the scope of 1.0 μ m～10.0 μ m, wherein be preferably in the scope of 1.2 μ m～5.0 μ m, You Jia is in the scope of 1.5 μ m～4.0 μ m.Be in above-mentioned scope by the thickness that makes resist, can utilize phase-shift mask of the present invention to form the photoresistance pattern with required form.
Moreover the resist using in the lump with phase-shift mask of the present invention is not limited to above-mentioned situation.
[embodiment]
< is about translucent phase shift region >
(embodiment 1)
Fig. 4 (a) is the curve of result of the variation gained that distributes of the exposure intensity while utilizing exposure emulation to obtain to make the situation that the width W in phase shift region changes.Fig. 4 (b) is the curve of the central portion of the light intensity distributions of Watch with magnifier diagram 4 (a).Fig. 4 (c) is the light intensity of each exposure intensity distribution central portion of variation and the curve of the height at side peak representing for the width W in Fig. 4 (a) phase shift region.
Fig. 5 utilize exposure simulation to utilize the exposure intensity of large-scale phase-shift mask of the present invention distribute, with the exposure intensity of binary mask that the utilizes identical patterns curve comparing that distributes.
Fig. 4 (a) is that the light intensity distributions (being called exposure intensity distribution) for parameter and on the imaging surface of the one side that utilizes exposure simulation to utilize to be surrounded through region 3 comprising as shown in Fig. 5 (a) when the large-scale phase-shift mask 50 in the foursquare translucent phase shift region 4 of W exposes is obtained taking the width W in translucent phase shift region, and draws the curve of exposure intensity distribution gained along CC section.The width W of the parameter of simulating as exposure is to select 10 μ m, 8 μ m, 6 μ m, 5 μ m, 4 μ m, 3 μ m, 2 μ m, 1 μ m.Exposure wavelength in exposure simulation is 365nm, the optical condition of exposure device is the condition of setting the liquid crystal exposure apparatus (Nikon (Nikon) system) of the poly-lens projection optical system of carrying promising lens projection exposure mode, and the transmittance of translucent phase shift film is made as 5.2%.The outermost of the curve that the expression exposure intensity of Fig. 4 (a), (b) distributes is to be the curve that 10 μ m are corresponding with the width W in translucent phase shift region, below, nested shape ground is arranged side by side to the inside successively to represent to be distributed to the curve of the concavity that the exposure intensity corresponding with width 1 μ m distribute by the exposure intensity corresponding with width 8 μ m.
Exposure intensity 51 on the imaging surface corresponding with the central portion in translucent phase shift region 4 is in the width W in translucent phase shift region 4 is the scope of 10 μ m to 3 μ m, in the time that the exposure intensity that sees through region is made as to 100%, show 4% to 10% exposure intensity, there is roughly fixing light shielding ability.If width W becomes 2 μ m, the exposure intensity of central portion becomes 23%, if width W becomes 1 μ m, the exposure intensity of central portion becomes 71%, and light shielding ability reduces.This situation is shown in to the broken line curve 52 of Fig. 4 (c).
With reference to Fig. 4 (b), the height at the side peak that the exposure intensity of translucent phase-shift mask distributes is in the time certainly seeing through region 3 and observe successively exposure intensity to translucent phase shift region 4 and distribute, and utilizes the transmittance of initial minimal value 53, obtains with the absolute value 55 of the difference of the transmittance of next maximum value 54.The width W that makes translucent phase shift region 4 is changed to 1 μ m and obtains the broken line curve 56 that the results are shown in Fig. 4 (c) of the height gained at side peak from 10 μ m.The height at side peak shows the fixed value of 3 left and right of about percentage in the width W in translucent phase shift region is the scope of 10 μ m to 5 μ m, width is 5 μ m when following, and side peak heights reduces, if width W is 4 μ m to 1 μ m, do not observe side peak, the height at side peak is zero.
Sum up above exposure analog result, if due to the width W in translucent phase shift region is made as below 5 μ m, the height at side peak reduces, so can alleviate following problem,, the recess on the resist surface causing because of the impact at side peak or resist are residual etc. is judged as defect in the inspection of photoresistance pattern, and becomes the obstacle of semiconductor production step.And then, by the width W in translucent phase shift region is made as below 4 μ m, and do not produce side peak (height at side peak is zero), thereby eliminate the problem of the above-mentioned semiconductor production step causing because of side peak.On the other hand, if the width in translucent phase shift region is made as to 2 μ m, without side peak, but the central light intensity more greatly 23% that exposure intensity distributes, the in the use essential exposure imaging condition of adjusting.And then in the time that the width in phase shift region is the situation of 1 μ m, the central light intensity that exposure intensity distributes reaches 71%, hide rotary light performance and reduce significantly, so be not suitable for practicality.Wherein, above result is about translucent phase-shift pattern is made as to foursquare situation, in the time that phase-shift pattern is made as to the situation in line and gap, even if the width in translucent phase shift region is made as to 1 μ m, the light intensity of region central portion is also 30%, under the adjustment of exposure, development conditions, can use.This situation is represented with embodiment 2.
(exposure simulation result and exposure intensity distributed model)
The exposure intensity of utilization shown in key diagram 4 (a), (b) exposure simulation distributes, with relation at Fig. 1, exposure intensity distributed model illustrated in fig. 2.The shape of the schematic curve 26 that exposure intensity when situation that the peak value of the explanation secondary lobe of Fig. 2 (b) is fully separated by distributes are exposure intensities along with from see through region to translucent phase shift region near and reduce, after exposure intensity becomes zero, form side peak 29a, 29b as maximum value.On the other hand, in Fig. 4 (b), the width W in translucent phase shift region be the exposure intensity of 10 μ m distribute be exposure intensity along with from see through region to translucent phase shift region near reducing, obtain after minimal value at exposure intensity, there is side peak 54a, 54b, the schematic curve 26 that utilizes the feature of the curve of exposure emulation to distribute with explanation exposure intensity is fully consistent, and noncontradictory in the explanation model that the exposure intensity in Fig. 1, Fig. 2 distributes, so can say comparatively good.Moreover non-vanishing as the schematic diagram that the minimal value of the exposure intensity in exposure simulation distributes as exposure intensity is deviation (being aberration) due to the ideal performance from imaging len.
Next, obtain the distance at the Zhi Ce peak, border from translucent phase shift region of exposure intensity distribution according to exposure analog result, the height of obtaining side peak transfers the width W p in the translucent phase shift region of minimizing to.Because the border in translucent phase shift region is positioned at the position of 8.5 μ m and 16.5 μ m at imaging surface, the position of maximum value 54a, 54b that exposure intensity in emulation distributes is 11.1 μ m and 13.8 μ m, so be 2.8 μ m from the distance at the Zhi Ce peak, border in translucent phase shift region.Be under the configuration as overlapping in the peak value (phase reversal) of secondary lobe of exposure light in the width W in translucent phase shift region, the height maximum (state shown in Fig. 2 (b)) at side peak, if width W is little compared with it, the positive part of secondary lobe is overlapping more, and the height at side peak reduces., in the width W in translucent phase shift region, in 2 times of narrow scopes (W < Wp) of the distance at Zhi Ce peak, border, the height at side peak reduces.Because the distance from Zhi Ce peak, border of obtaining in exposure simulation is 2.8 μ m, so the overlapping width W of the peak value of secondary lobe is 5.6 μ m.According to the exposure analog result of Fig. 4 (c), the width W p that the height at side peak starts the translucent phase shift region of reducing is 5 μ m, consistent with the value 5.6 μ m that calculate according to the distance from Zhi Ce peak, border.
(contrast of embodiment 1 is improved effect)
Fig. 5 is the improvement of contrast of the translucent phase-shift mask while utilizing exposure simulation to be 4 μ m to becoming the width W distributing without the good exposure intensity at side peak and the result that binary mask compares.To distribute and be shown in the solid line of Fig. 5 (b) along the exposure intensity on the imaging surface that comprises the CC section that is the phase-shift mask in the foursquare translucent phase shift region of 4 μ m on one side shown in Fig. 5 (a).Be shown in the dotted line of Fig. 5 (b) by comprising that exposure intensity on the imaging surface of binary mask of foursquare lightproof area of same size distributes.Judge according to curve, the exposure intensity that the width that the exposure intensity of known binary mask distributes is narrower than phase-shift mask distributes, and pattern is thinner.Particularly, be 30% if sensitization level is made as to exposure intensity, the width of the exposing patterns of large-scale phase-shift mask is 4.1 μ m, on the other hand, the width of the exposing patterns under the identical sensitization level of binary mask is 3.7 μ m.That is, the decline precipitous (even contrast raising) that translucent phase-shift mask of the present invention distributes the exposure intensity of pattern boundaries, and have the effect that prevents the pattern width variation that utilizes exposure to carry out transfer printing.
(embodiment 2)
Fig. 6 is the key diagram that the effect that promotes of contrast that the exposure intensity of large-scale phase-shift mask of the present invention is distributed and previous binary mask compare.Fig. 6 (a) represents the line of large-scale phase-shift mask of the present invention and the planimetric map of gap (L/S) pattern, (b) be the line of binary mask and the planimetric map of gap pattern representing as prior art, be (c) comparison (a) with (b) shown in the imaging surface of mask on the figure that distributes of exposure intensity.
Again, table 1 is the table that the effect that promotes of contrast that the exposure intensity of large-scale phase-shift mask of the present invention is distributed and previous binary mask compare.
The pattern of the large-scale phase-shift mask of the present invention of Fig. 6 (a) is line and the gap pattern of 4 μ m spacing, and the width W in translucent phase shift region 3 is 1 μ m, and the width a that sees through region 4 arranging adjacently in the both sides in translucent phase shift region 3 is 3 μ m.The transmittance of translucent phase shift film is 5.2%, and phase place is with respect to the light reversion π (180 degree) by seeing through region.Moreover transmittance is to be made as 100% and calculated by seeing through the transmittance in region 6.
The pattern of 1 the binary mask as a comparative example of Fig. 6 (b) is line and the gap pattern of 4 μ m spacing, and the width in the width of lightproof area 63 and translucent phase shift region 3 is all 1 μ m, and the width that sees through region 64 is 3 μ m.
Fig. 6 (c) obtains and overlapping earth's surface shows the curve that the exposure intensity on the imaging surface of the result of utilizing the binary mask 61 of phase-shift mask 60 of the present invention and comparative example 1 and expose by light exposure device distributes by simulation, and the light source of exposure device is to calculate with 3 wavelength hybrid light sources of g ray, h ray, i ray.The longitudinal axis of curve is the maximal value of the exposure intensity on imaging surface to be normalized to 1 represent, the transverse axis of curve is expressed as the position in image planes.The exposure intensity of the position corresponding with the AA section of the large-scale phase-shift mask shown in Fig. 6 (a) is distributed and is shown in exposure intensity distribution curve 65.The exposure intensity of the position corresponding with BB section 1 binary mask as a comparative example shown in Fig. 6 (b) is distributed and is shown in exposure intensity distribution curve 66 again.
The maximal value of the light intensity distributions of the exposure intensity distribution curve 65 of the large-scale phase-shift mask shown in Fig. 6 (c) is 0.740, and minimum value is 0.306, is 0.434 as the contrast of the difference of maximal value and minimum value.On the other hand, be 0.782 as the maximal value of the light intensity distributions of the exposure light intensity distributions curve 66 of the binary mask of prior art, minimum value is 0.399, is 0.383 as the contrast of the difference of maximal value and minimum value.That is, previously the contrast of the exposure light on the imaging surface of binary mask was 0.383, and on the other hand, the contrast of the exposure light of large-scale phase-shift mask of the present invention is 0.434, and contrast exceeds 0.051, with the ratio of contrast, can be observed approximately 13% improvement.Be recorded in the effect of large-scale phase-shift mask of table 1 blanket this result.
[table 1]
The effect of large-scale phase-shift mask
According to above exposure analog result, the present invention can and suitably configure the width in translucent phase shift region by restriction in large-scale mask, and improves the contrast that the exposure intensity on imaging surface distributes, thereby stably forms finer pattern.
< is about phase shift region, edge >
(contrast distributing about exposure intensity)
Figure 12 is the key diagram that the effect that promotes of contrast that the exposure intensity in the phase shift region, edge (reference example 1) in large-scale phase-shift mask of the present invention is distributed and previous binary mask (comparative example 2) compare.Figure 12 (a) is the line of the mask (reference example 1) that represents to comprise phase shift region, edge and the planimetric map of gap pattern, Figure 12 (b) represents the line of the binary mask (comparative example 2) as prior art and the planimetric map of gap pattern, and Figure 12 (c) is to the figure comparing that distributes of the exposure intensity on the imaging surface of the mask shown in Figure 12 (a) and Figure 12 (b).
Again, table 1 is the table that the effect that promotes of contrast that the exposure intensity of the mask (reference example 1) to comprising phase shift region, edge distributes and previous binary mask (comparative example 2) compare.
The pattern in as a reference example 1 the phase shift region, edge of Figure 12 (a) is line and the gap pattern of 4 μ m spacing, is 3 μ m through the width a in region 3.The width b in the 2nd translucent phase shift region 104 arranging adjacently in the both sides that see through region 3 is 0.4 μ m, and transmittance is 5.2%, and phase place is with π (180 degree) reversion.Again, the width of lightproof area 103 is 0.2 μ m, and transmittance is 0%.Moreover the transmittance in each region is to be made as 100% and calculated by seeing through the transmittance in region 3.
The pattern of 2 the binary mask as a comparative example of Figure 12 (b) is line and the gap pattern of 4 μ m spacing, and the width d that sees through region 64 is 3 μ m, and the width e of lightproof area 63 is 1 μ m.
Figure 12 (c) is the curve that represents to obtain by emulation the result of the exposure result of utilizing exposure device, and the light source of exposure device is to calculate with 3 wavelength hybrid light sources of g ray, h ray, i ray.The longitudinal axis of curve is the maximal value of the exposure light intensity that sees through region on imaging surface to be normalized to 1 represent, the transverse axis of curve is expressed as the position in image planes.The exposure light intensity distributions of the large-scale phase-shift mask of the position corresponding with the AA section of Figure 12 (a) is shown in to exposure light intensity distributions curve 131.The exposure light intensity distributions of the binary mask of the position corresponding with the BB section of Figure 12 (b) is shown in to exposure light intensity distributions curve 132 again.
The maximal value of the light intensity distributions of the large-scale phase-shift mask exposure light intensity distributions curve 131 shown in Figure 12 (c) is 0.747, and minimum value is 0.324, is 0.423 as the contrast of the difference of maximal value and minimum value.On the other hand, be 0.782 as the maximal value of the light intensity distributions of the exposure light intensity distributions curve 132 of the binary mask of prior art, minimum value is 0.399, is 0.383 as the contrast of the difference of maximal value and minimum value.That is, previously the contrast of the exposure light on the imaging surface of binary mask was 0.383, and on the other hand, the contrast of the exposure light of large-scale phase-shift mask of the present invention is 0.423, and contrast exceeds 0.04, with the ratio of contrast, can be observed approximately 10% improvement.Be documented in the effect of large-scale phase-shift mask of table 2 blanket this result.
[table 2]
The effect of large-scale phase-shift mask
According to above exposure analog result, the present invention can suitably configure the 2nd translucent phase shift region in large-scale mask, improves the contrast that the exposure intensity on imaging surface distributes, thereby stably forms finer pattern.
(about the relation of drawing pattern of resolution limit and the phase-shift mask of exposure machine)
The making > of < phase-shift mask
Preparation stacks gradually the commercially available photomask blank of the chromium oxide film (anti-reflective film) that chromium film (photomask) that the synthetic quartz that thickness is 10mm (transparency carrier), thickness are 100nm and thickness are 25nm, on anti-reflective film, be coated with applicable photonasty resist, after coating, toast given time, and form the photomask photoresistance film of even thickness.Next, by laser scanning picture device, above-mentioned photomask is drawn to the pattern of lightproof area with photoresistance film, and developed, and form photomask resist.
Next, be used in the wet etchant that was added with chloric acid in ammonium ceric nitrate, etching is also removed the anti-reflective film and the photomask that expose with resist from photomask, remaining resist is peeled off and is removed, and obtain the photomask of shape and the substrate of anti-reflective film that are formed as lightproof area with pattern.
Next, utilize sputtering method to make nitrogen chromium oxide film (the 2nd translucent phase shift film) in whole the film forming of being with through the photomask of pattern formation and the substrate of anti-reflective film.
Next, form step by the 2nd pattern, using itself and lightproof area position alignment as the photomask pattern of lower floor, utilize the formation method identical with photomask resist, formation the 2nd translucent phase shift film photoresistance film.Next, by laser beam describing device, the 2nd translucent phase shift film is drawn after the pattern that makes the region that the 2nd translucent phase shift region aims at lightproof area with photoresistance film, developed, and obtain the 2nd translucent phase shift film resist forming through pattern.
Next, with above-mentioned photomask and similarly etching of anti-reflective film and remove the 2nd translucent phase shift film exposing with resist from the 2nd translucent phase shift film, and obtain pattern and be processed as the 2nd translucent phase shift film of the shape that makes photomask pattern and the 2nd translucent phase shift regional alignment.Next the photoresistance film of, the 2nd remaining translucent phase shift film being used is peeled off, is removed.By above step, and obtain dispose through region (live width be 1.9 μ m), the 2nd translucent phase shift region (live width be 2.0 μ m) and lightproof area and stack gradually anti-reflective film and the large-scale phase-shift mask of the 2nd translucent phase shift film in lightproof area on photomask.
The making > of < photoresistance pattern
Utilize above-mentioned phase-shift mask, and the exposure machine that the Nikon that utilizes resolution pole to be limited to 3 μ m manufactures, be that the resist (AZ1500) of 1.6 μ m carries out pattern exposure to being formed on thickness on glass baseplate, and carry out development treatment, result can form the photoresistance pattern of 1.9 μ m.
(about the width in the 2nd translucent phase shift region in phase-shift mask)
Figure 13 is the planimetric map that represents the pattern of the large-scale phase-shift mask that comprises phase shift region, edge, Figure 14 is the figure that represents that the exposure intensity on the imaging surface of the large-scale phase-shift mask shown in Figure 13 distributes, Figure 15 is the enlarged drawing of the C part of Figure 14, and Figure 16 is the enlarged drawing of the D part of Figure 14.
The exposure intensity distribution (light intensity) of the exposure machine that utilizes the manufacture of Nikon company during to following situation is simulated, , as large-scale phase-shift mask, and the width that sees through region is made as to 5 μ m, the width b in the 2nd translucent phase shift region is made as to 0.25 μ m (reference example 3), 0.5 μ m (reference example 4), 0.75 μ m (reference example 5), 1.0 μ m (reference example 6), 1.5 μ m (reference example 7), 2.0 μ m (reference example 8), 2.5 μ m (reference example 9), 3.0 μ m (reference example 10), 3.5 μ m (reference example 11), and 4.0 μ m (reference example 12).Moreover, make the simulated conditions except the pattern of above-mentioned large-scale phase-shift mask identical with reference example 1.Show the result in Figure 14～Figure 16.
Exposure intensity shown in Figure 15 is less, represent that the waveform shown in Figure 14 is more precipitous, about the phase shift effect of the position of the pattern edge of large-scale phase-shift mask, if the width in the 2nd translucent phase shift region exceedes 2.0 μ m, do not observe more obvious effect (phase shift effect reaches capacity).
Again, as shown in figure 16, along with the width in the 2nd translucent phase shift region becomes large, it is large that the value at side peak becomes.
In the present invention, can be according to the sensitivity of resist, the mode impacting with the non-confrontational erosion agent in side peak is set the width in the 2nd translucent phase shift region.
About the width of this kind of phase shift, with regard to forming the actual achievement of the resist using when tft array substrate, be preferably the exposure intensity that is made as side peak and be width below 5%, in the scope of 0.25 μ m～3.5 μ m.
Symbol description
1 transparency carrier
2 translucent phase shift films
3,3a, 3b see through region
4 translucent phase shift regions
5 exposure light
10,40,50,60 large-scale phase-shift masks
11a, 11b are through the optical ampeitude of the light through region
11c sees through the optical ampeitude of the light in translucent phase shift region
12a, 12b are through the optical ampeitude on imaging surface of the light through region
The peak value of the secondary lobe of 13a, 13b optical ampeitude
14, the optical ampeitude on imaging surface of 24,34 light through translucent phase shift region
15, the optical ampeitude on imaging surface of 25,35 light through large-scale phase-shift mask
16, the light intensity distributions on imaging surface of 26,36,56,66 light through large-scale phase-shift mask
17, the light intensity distributions on imaging surface of 27,37,57,67 light through binary mask
18, the contrast of 28,38 large-scale phase-shift masks promotes effect
The peak value of the optical ampeitude on 21a, 21b, 31 imaging surfaces
The peak value (side peak) of the light intensity distributions on 29a, 29b, 39 imaging surfaces
41 photomask blanks
42 resists

Claims (6)

1. a large-scale phase-shift mask, it comprises transparency carrier, and be formed on the translucent translucent phase shift film on above-mentioned transparency carrier, comprise the region that sees through of having exposed above-mentioned transparency carrier, and on above-mentioned transparency carrier, be only provided with the translucent phase shift region of above-mentioned phase shift film, and comprise and dispose adjacently the above-mentioned mask pattern that sees through region and above-mentioned translucent phase shift region, and see through the phase place of exposure light in above-mentioned translucent phase shift region with respect to seeing through the above-mentioned phase reversal of exposure light that sees through region, in the time that the transmittance of the above-mentioned exposure light that sees through region is made as to 100%, the transmittance of the exposure light in above-mentioned translucent phase shift region is the value of 4% to 30% scope.
2. large-scale phase-shift mask as claimed in claim 1, wherein,
The both sides that are included in above-mentioned translucent phase shift region dispose the above-mentioned pattern that sees through region adjacently, and the width in above-mentioned translucent phase shift region is the width of the scope of 1 μ m to 5 μ m.
3. large-scale phase-shift mask as claimed in claim 1 or 2, wherein,
Above-mentioned translucent phase shift film is the individual layer that contains chromium and chromium compound or the structure of 2 layers.
4. the large-scale phase-shift mask as described in any one in claim the 1 to 3, wherein,
The thickness of above-mentioned translucent phase shift film is the thickness of the scope of 0.1 μ m to 0.14 μ m.
5. the large-scale phase-shift mask as described in any one in claim the 1 to 4, wherein,
Comprise the photomask being formed on above-mentioned transparency carrier, and translucent the 2nd translucent phase shift film forming to cover the mode of above-mentioned photomask, and comprise the mask pattern that disposes lightproof area and the 2nd translucent phase shift region, stacked above-mentioned photomask and above-mentioned the 2nd translucent phase shift film of being provided with of this lightproof area, the 2nd translucent phase shift region is arranged on above-mentioned lightproof area and above-mentionedly sees through between region and be only provided with above-mentioned the 2nd translucent phase shift film, and see through the phase place of exposure light in above-mentioned the 2nd translucent phase shift region with respect to seeing through the above-mentioned phase reversal of exposure light that sees through region.
6. a manufacture method for large-scale phase-shift mask, it comprises the following steps:
The step of the blank of preparation with photonasty resist, to be that the one side at transparency carrier is stacked be coated with photonasty resist taking chromium and chromium compound and obtain this blank with photonasty resist on the blank that the translucent phase shift film of material forms; And
Utilize describing device by the extremely above-mentioned blank with photonasty resist of required pattern exposure, after developing, carry out Wet-type etching, remove photonasty resist, and make above-mentioned translucent phase shift film form the step of pattern.
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