CN101310220A

CN101310220A - Mask blank and photo mask

Info

Publication number: CN101310220A
Application number: CNA2006800427265A
Authority: CN
Inventors: 三井胜
Original assignee: Hoya Corp
Current assignee: Hoya Corp
Priority date: 2005-11-16
Filing date: 2006-11-15
Publication date: 2008-11-19
Anticipated expiration: 2026-11-15
Also published as: KR20080068128A; KR101056592B1; KR20110013573A; CN101310220B; WO2007058199A1

Abstract

To provide a large-size mask and a mask blank for FPD for manufacturing an FPD device appropriate for multi-color wave exposure. [MEANS FOR SOLVING PROBLEMS] A mask blank includes a light shielding film having a lower layer portion having the light shielding function and an upper layer portion having the reflection preventing function formed on a translucent substrate. The light shielding film is controlled so that a fluctuation width of the film surface reflectance is below 1% in a wavelength band at least from i-line to g-line emitted from an ultra high pressure mercury lamp.

Description

Mask base plate and photomask

Technical field

The present invention relates to mask base plate (mask blank) and photomask (photo mask), particularly be used to make the FPD device mask base plate (base plate that photomask is used), adopt photomask (transfer mask) that this mask base plate makes etc.

Background technology

In recent years, with in the field of mask, attempt adopting gray scale mask, cut down the number (Non-Patent Document 1) of mask with semi-transparency field (being so-called gray scale part) at large-scale FPD.

Here, shown in Fig. 5 (1) and Fig. 6 (1), gray scale mask has light shielding part 1 and sees through portion 2 and the semi-transparency field is a gray scale portion 3 on transparency carrier.Gray scale portion 3 has the function of adjusting transit dose, for example, shown in Fig. 5 (1), be to have formed the field of gray scale mask with semi-transparency film (semi-transparency film) 3a`, perhaps shown in Fig. 6 (1), it is the field that has formed greyscale pattern (large LCD of use gray scale mask following fine light-shielding pattern 3a of the imaging limit of exposure machine and the fine 3b of portion of seeing through), the formation purpose is: the transit dose that reduces the light in these fields of seeing through, reduce the exposure that cause in this field, the film thickness monitoring after will reducing the thickness after the video picture of photoresist that should the field is to expectation value.

Large-scale gray scale mask carried Miller projection (Miller Projection) mode or use when using on the large-scale exposure device of lens mode of lens, whole as the exposure light that sees through gray scale portion 3, make exposure become not enough, therefore through the only attenuation of thickness of the positive photoresist of these gray scale portion 3 exposures, and remain on the substrate.Promptly, because the difference of exposure, photoresist can the part corresponding with common light shielding part 1 and with gray scale portion 3 corresponding part on, difference appears on the dissolubility to developer solution, therefore, shown in Fig. 5 (2) and Fig. 6 (2), the photoresist shape after the development, the part 1` corresponding with common light shielding part 1 for example is about 1 μ m; The part 3` corresponding with gray scale portion 3 for example is about 0.4 ~ 0.5 μ m; The part corresponding with seeing through portion 2 becomes the part 2` of no photoresist.And, on the part 2` of no photoresist, carry out the 1st etching of processed substrate, photoresist by the corresponding thin part 3` of removal such as ashing and gray scale portion 3, carry out the 2nd etching in this part, originally the operation that needed 2 masks to carry out by 1 mask thus, thus the mask number cut down.

Non-Patent Document 1: " monthly magazine FPD Intellgence ", p.31-35, in May, 1999

Non-Patent Document 2: " talking about photomask technology ", Tian Biangong, method unit contains for a long time, bamboo ocean work, and census of manufacturing proceedings, " the 4th chapter LCD with the reality of photomask " are p.151-180

; be used to make the LSI mask of the semiconductor devices of microprocessor, semiconductor memory, system LSI etc.; its full-size is that 6 inches degree are square, and is small-sized relatively, is equipped in the reduced projection exposure device that adopts reduced projection (shot stepper) mode step by step more.With in the mask, as being transferred substrate, serves as that final form use to be cut to a plurality of chips with Silicon Wafer at this LSI.With in the mask, the imaging limit should be broken at this LSI, the short wavelengthization of exposure wavelength can be realized by the exposure wavelength decision.Here, with in the mask,, can use monochromatic exposure light (exposure light of single wavelength) at LSI from the viewpoint that scioptics system gets rid of chromatic aberation and improves imaging thus.About the short wavelengthization of this LSI, develop into g line (436nm), i line (365nm), KrF excimer laser (248nm), the ArF excimer laser (193nm) of ultrahigh pressure mercury lamp with the exposure wavelength of the monochrome of mask.In addition, make and be formed on LSI and reach (minimum feature that is formed on the pattern on the wafer is about 0.07 μ m) about 0.26 μ m with the minimum feature of the mask pattern on the mask.

Relative therewith, FPD is equipped on the Miller projection (by the scan exposure mode with large-scale mask (Flat Panel Display), Deng a times projection exposure) when the exposure device of mode uses, (1) only can carry out exposure through mask by reflective optical system, therefore can not occur as LSI with mask, owing to the problem of lens combination between the chromatic aberation that wherein produces, and (2) are under present situation, study the influence (based on the influence that sees through light and catoptrical interference and chromatic aberation etc.) of polychrome ripple exposure (multi-wavelength exposure) with a plurality of wavelength, compare the words of having guaranteed big exposure light intensity with monochromatic wave exposure (single wavelength exposure), from comprehensive production face is favourable, in addition, when the large-scale exposure device that is equipped on the lens mode uses, because above-mentioned (2) described situation etc., implement to utilize the polychrome ripple exposure in wide wavelength band territory of the i line～g line of ultrahigh pressure mercury lamp.

In addition, FPD with large-scale mask base plate in, compare with the situation that substrate size is little, when substrate size is big, owing to make the reason of the limit surface (being derived from the limit surface of manufacture method and manufacturing installation) on the principle, and the reason of the change of creating conditions (process change), in the face and the various characteristics between substrate (film forms, membranous, transmitance, reflectivity, optical concentration, etching characteristic, other, optical characteristics, thickness etc.) be easy to generate inequality, therefore, be difficult to make in a large amount of, the face and the uniform mask base plate of various characteristics between substrate.This feature becomes more meticulous along with further maximization, the height of FPD and the trend that occurs increasing.

In face and under the big situation of the deviation of various characteristics between substrate, following problem can appear.

(1) the big product of various characteristics deviation from the big this point of deviation, can not be called high-qualityly, can not be called good on the performance face.

(2) when the deviation of various characteristics is big, be difficult to make product up to specification, also be difficult to a large amount of products up to specification of producing.

(3) because the deviation of various characteristics is big, out-of-spec product can occur, cause productivity (yield rate) poor.

(4) when the deviation of various characteristics is big, need slow down specification limits correspondingly.Therefore, can not realize high standardization, be difficult to tackle high standardization.

Moreover, be formed on FPD with the minimum feature of the pattern on the large-scale mask be about 1 μ m below, be formed on the minimum feature that is transferred with the pattern on the large-size glass substrate and be about 2～3 μ m, greater than the minimum feature of the LSI of tip.But, large-area FPD is used as 1 product, to compare with LSI, its final form is a large tracts of land, needs all a plurality of elements all to play a role.Therefore, do not allow to have the out-of-spec defective that hinders defective that all elements play a role and the possibility that is considered to have obstruction.So, in the FPD product, need to realize large tracts of land and zero defect, but reach the deviation of the various characteristics between substrate in the face in the large-scale mask when big as FPD that existence is difficult to realize the feature of FPD with high-qualityization of large-scale mask and large tracts of land FPD product and raising yield rate etc.This feature is along with further maximization, the height of FPD becomes more meticulous and the trend that occurs increasing.

As mentioned above, FPD with large-scale mask in, based on the difference of mask environment for use and the difference of mask size etc., we can say can require (promptly having necessity of discussion) it has at LSI and can not require in mask the characteristic of (promptly do not have inquire into necessity).

About based on the FPD of the generations such as difference of the environment for use of such mask with the distinctive characteristic that requires of large-scale mask, the present inventor person is conceived to the exposure of polychrome ripple.

So, a plurality of wavelength advantage that (exposure of polychrome ripple) handle of exposing is: the exposure (monochromatic wave exposure) that the light intensity of exposure can be carried out greater than single wavelength.For example with only for the i line or only compare for the exposure of the monochromatic wave of g line, expose to the light in the wavelength band territory of g line by the i line that lies across that comprises the h line, exposure intensity is big.Therefore, can improve the productivity of device.

For example, more large-scale display device such as FPD device adopts and waits a times exposure method to make.Compare with the exposure method that dwindles that in the manufacturing of LSI device etc., adopts, in waiting times exposure method, shine exposure light on the device side to inject intensity little, therefore having can be by utilizing a plurality of wavelength, to shining the advantage that intensity is replenished of injecting of exposure light on the device side.

On the other hand, when utilizing a plurality of wavelength to carry out exposure-processed,, therefore need fully to suppress the reflectivity of mask surface because the light intensity of exposure is big.

This is after being reflected because of a part that shines the exposure light on the device side, be injected into the light (light that returns from device side one side) of mask surface from device side one side, the reflected light of masked surface reflection also becomes the light with a plurality of wavelength, this light is injected on the device side with exposure light once more, and therefore suitable pattern forms and hindered.

For example, because the area of the display device that FPD device etc. are large-scale is big, therefore special requirement are carried out uniform exposure-processed in face, but in a plurality of wavelength exposures that utilize a plurality of wavelength, catoptrical light intensity is big, be difficult to fully suppress, therefore become and (for example: the essential factor of the Gong Geiing FPD device) hinder high-quality goods.

In addition, under the situation of gray scale mask, the reflected light of the mask surface that the back light by device one side that gray scale portion and light shielding part two places produce causes is injected into device one side, therefore also might cause and make difficulty.

Summary of the invention

The objective of the invention is to, find out the problem of following the exposure of polychrome ripple to occur, propose corresponding solution.

Based on the present inventor person's research, draw if in the scope in the wavelength band territory of the exposure light that is used for exposure-processed, the mask that the reflectivity of mask surface is suppressed at wide band can address these problems.

In addition, based on discovering of the present inventor person, the mask that forms in the stacked upper layer part that has the lower layer part of shade function and on this lower layer part, form on the light-transmitting substrate with anti-reflective function, when with the composition of described lower layer part and described upper layer part adjacent part,, when having the composition inclination of continuity migration, described upper layer part can address these problems from described lower layer part.

In addition, based on discovering of the present inventor person, has the lower layer part of shade function and under the situation of the upper layer part that has anti-reflective function on this lower layer part in formation, utilize online sputtering method etc., handle by continuous formation, can from the lower layer part to the upper layer part, form such composition oblique structure well.

Moreover the present inventor person is conceived to FPD with distinctive polychrome ripple exposure in the large-scale mask manufacturing, studies with the distinctive characteristic that requires of large-scale mask at the FPD that is suitable for this polychrome ripple exposure.

Found that the following fact.

(1) from exposure light source be ultrahigh pressure mercury lamp radiation i line, h line, g line exposure light intensity (relative intensity) about equally.More particularly, the exposure light intensity (relative intensity) of i line, h line, g line but is compared with the i line at two ends, the intensity of g line about equally, the intensity lower slightly (with reference to figure 1) of the h line of central authorities.

That is,, need either party of the equal i of attention line, h line, g line, can think for when the mask exposure from relative intensity, effect that can corresponding relative intensity performance, for example the face reflectivity that produces of antireflection film etc. all needs to give equal attention.

Here, relative intensity at corresponding i line, h line, g line shows on, when considering the face reflectivity of antireflection film, the branch light curve (spectral reflectance curve, reflectance curve) of the face reflectivity R that the antireflection film of certain thickness produces is the function of wavelength X, can use R=f (λ) expression.The branch light curve of this face reflectivity R, mainly by membrane material, film form, membranous, create conditions, decision such as manufacturing installation.On the other hand, face reflectivity R is relevant with R=f (λ) and thickness, changes with their variation.

In addition, about face reflectivity R,, do not having problems on the performance of antireflection and on the specification as long as below certain value.Therefore, in the wavelength band territory of i line～g line, even the amplitude of fluctuation of the branch light curve of face reflectivity R (maximum reflectivity of the reflectivity in each wavelength and minimum reflectance poor) big (dividing the crooked strong of light curve), as long as the maximal value of the face reflectivity R in the wavelength band territory of i line～g line is below the certain value, not have problems on antireflection property.

Yet the exposure light intensity of considering i line, h line, g line even be preferably as can be known for either party of i line, h line, g line, can realize face antiradar reflectivity (low face reflectivity) about equally about equally.

(2) in fact can produce the film that has face reflectivity (for example: in i line, h line, the g line, the mutual difference of each reflectivity is lower than 1%) about equally for i line, h line, g line as can be known.

(3) use in the mask at the large-scale FPD that can be used in the exposure of polychrome ripple as can be known, by will be for relative intensity i line, h line, g line about equally, film with face reflectivity about equally, be applied to mask base plate and mask, the situation of the film big with adopting the change width of cloth is compared, make in the face easily in a large number and the uniform goods of face reflectivity between substrate, therefore, help to improve the quality of mask base plate and yield rate etc., and then, help to improve the quality of large tracts of land FPD goods and yield rate etc.

(4) with above-mentioned (1), (3) relevant, for example as shown in Figure 3, at least be for the i line by optical design, the h line, the g line, has about equally face reflectivity, under the situation of the film that the amplitude of fluctuation of face reflectivity is little (for example amplitude of fluctuation is lower than 1%), be preferably in comprising the wide wavelength band territory of i line ~ g line, the film that the amplitude of fluctuation of face reflectivity is little (for example by optical design for being in the wavelength band territory of 350nm～450nm at wavelength, the amplitude of fluctuation of face reflectivity is lower than 2%, and the film of making) under the situation, for the change of creating conditions (process change) with the change formed of the film that produces and the change of thickness etc. thereupon, even divide light curve (spectral reflectance curve, reflectance curve) left and right displacement up and down, therefore can not cause spectral reflectance (reflectivity in each wavelength) that big change takes place, the having good uniformity of spectral reflectance (reflectivity in each wavelength) yet.Therefore, produce the goods that have good uniformity of spectral reflectance (reflectivity in each wavelength) as can be known easily, in a large number, in addition, in large quantities, high finished product rate produce mask base plate and the mask of k up to specification easily.

Relative therewith, for example as shown in Figure 3, in above-mentioned wavelength band territory, when the change width of cloth H` of spectral reflectance (reflectivity in each wavelength) is big, change of forming for slightly the change of creating conditions (process change) and the film that produces thereupon and thickness change etc., divide light curve (spectral reflectance curve, reflectance curve) produces displacement about up and down, cause the significantly change of spectral reflectance (reflectivity in each wavelength) thus, so homogeneity variation of spectral reflectance (reflectivity in each wavelength), in addition, owing to divide light curve (spectral reflectance curve, reflectance curve) displacement, the ratio of specification k product is in addition increased, cause making difficulty and the productivity variation.Therefore, in fact little with changing width of cloth H situation is compared, and the words that do not reduce specification k just can not obtain good productivity.

(5) as mentioned above, even in the wavelength band territory of i line～g line, the amplitude of fluctuation of the branch light curve of face reflectivity R is big, as long as the maximal value of the branch light curve of the face reflectivity R in the wavelength band territory of i line～g line is not in-problem on the performance of antireflection below certain value.Yet, for example as shown in Figure 4, the amplitude of fluctuation of the spectral reflectance (reflectivity in each wavelength) in the preferred above-mentioned wavelength band territory is little, compare with the situation that amplitude of fluctuation is big, in the specification k, the k` that close at the above-mentioned wavelength band territory that lies across, under the situation in (can management of wavelengths band territory), become a standard that judges whether to make identical film with specification value k, the k` of the upper limit, lower limit.

(6) in addition, relevant with above-mentioned (2), in that find in fact can be with respect to i line, h line, g line, produce in the process of film of the face reflectivity that has about equally, obtain following opinion.

(i) words of the antireflection film of chromium oxide film class (for example CrO film individual layer etc.), when making it have function as antireflection film, can contain O (because the O in the film is many) in the film, the wavelength band territory of i line～g line, moreover in comprising the wideer wavelength band territory in described wavelength band territory, basically divide light curve (spectral reflectance curve, reflectance curve) bending is strong, in addition, at a minute light curve (spectral reflectance curve, reflectance curve) in, the width that becomes the wavelength band territory of minimum reflectance diminishes, and the amplitude of fluctuation of spectral reflectance (reflectivity in each wavelength) has the tendency that becomes big.

Here, also can consider by the antireflection film of chromium oxide film class (for example CrO film etc.) is made multilayer, thereby reduce the amplitude of fluctuation of the spectral reflectance (reflectivity in each wavelength) in the above-mentioned wavelength band territory, but when making multilayer, it is complicated that technology becomes, and also can cause the increase of film defective.

(ii) compare with the antireflection film of chromium oxide film class, in nitrogen chromium oxide film class (for example: in antireflection film CrON film etc.), the wavelength band territory of i line～g line, moreover in comprising the wideer wavelength band territory in described wavelength band territory, basically divide light curve (spectral reflectance curve, reflectance curve) bending is mild, be flat, but it is high-quality in order to reach a large amount of manufacturings, the purpose of uniform more (tighter specification) mask base plate and FPD, even the antireflection film of any nitrogen chromium oxide film, can not reach described purpose, and, no matter which type of light-proofness film the lower floor of the antireflection film of nitrogen chromium oxide film class is, can not reach described purpose.Therefore, need find out, use the antireflection film and the light-proofness film of the nitrogen chromium oxide film class that satisfies the specified requirements be suitable for reaching described purpose.Promptly, even the nitrogen chromium oxide film that membrane material is identical, but because the adjustment that film is formed, the selection of creating conditions, making position etc. and control, these are to the material of membranous control, light-proofness film etc., the position of peak base (Bottom Peak), the differences such as difference that film constitutes, and also have the situation that satisfies specified requirements and discontented toe fixed condition.

The inventive method has following formation.

(constitute 1) a kind of mask base plate that is used to make the FPD device, it has the light-proofness film on light-transmitting substrate, and this light-proofness film is made of lower layer part with shade function and upper layer part with anti-reflective function at least, and described mask base plate is characterised in that,

Described light-proofness film is the wavelength band territory of the scope from the i line to the g line at least of radiating from ultrahigh pressure mercury lamp, and the change width of cloth of face reflectivity is controlled in and is lower than 1% the interior film of scope.

(constitute 2) is characterized in that according to constituting the 1 described mask base plate that is used to make the FPD device, and described light-proofness film is that described face reflectivity is controlled in that to become minimum minimum reflectance be the film of the wavelength coverage of 380nm～430nm.

(constituting 3) is according to constituting the 1 or 2 described mask base plates that are used to make the FPD device, it is characterized in that, described light-proofness film is made of with the upper layer part with nitrogen chromium oxide class of anti-reflective function the lower layer part of the chromium carbide class with shade function, and described lower layer part and upper layer part are made as by optical design and satisfy above-mentioned important document.

(constituting 4) is according to constituting the 1 or 2 described mask base plates that are used to make the FPD device, it is characterized in that, described light-proofness film is by the basalis of chromium nitride class and have the lower layer part of chromium carbide class of shade function and the upper layer part with nitrogen chromium oxide class of anti-reflective function constitutes, and described basalis, lower layer part and upper layer part are made as by optical design and satisfy above-mentioned important document.

(constituting 5) a kind of mask base plate, it is characterized in that, by light-transmitting substrate, with the lower layer part that is formed on this substrate with shade function, and be formed on the upper layer part that has anti-reflective function on this lower layer part and be laminated, described mask base plate be described lower layer part and described upper layer part formed by pattern be treated as photomask after, when making device, the mask base plate that the photomask of the exposure light exposure-processed of involved a plurality of wavelength is used, the reflectance curve of described mask base plate constitutes with respect to light wavelength and is protruding curve downwards, and the minimal reflection of described reflectance curve commands troops to become in the wavelength band territory corresponding to described exposure light.

(constitute 6) mask base plate is to constitute 5 described mask base plates, it is characterized in that, the above g line of i line wavelength wavelength with interior wavelength band territory in, reflectivity becomes minimum.

(constituting 7) mask base plate is a formation 5 or constitute 6 described mask base plates, it is characterized in that reflectivity becomes minimum in h line wavelength in fact.

(constituting 8) mask base plate is to constitute each described mask base plate in 5～7, it is characterized in that, is no more than 13% corresponding to the maximum reflectivity in the wavelength band territory of described exposure light.

(constituting 9) mask base plate is to constitute each described mask base plate in 5～8, it is characterized in that, and be the mask base plate of using corresponding to the photomask of the exposure machine that waits times exposure-processed.

(constituting 10) a kind of photomask that is used to make the FPD device is characterized in that each described mask base plate manufacturing forms in the employing formation 1～4.

(constituting 11) a kind of photomask is characterized in that each described mask base plate manufacturing forms in the employing formation 5～9.

According to the present invention, can provide a kind of FPD that is applicable to polychrome ripple exposure with large-scale mask and mask base plate.

Description of drawings

Fig. 1 is the figure of expression as the beam split distribution of the ultrahigh pressure mercury lamp of exposure light source.

Fig. 2 is the figure of the branch light curve (spectral reflectance curve, reflectance curve) of the light-proofness film with anti-reflective function made by embodiment 1～3 and comparative example 1 of expression.

Fig. 3 is that expression is used for the figure that the mode to the branch light curve (spectral reflectance curve, reflectance curve) of the light-proofness film with anti-reflective function describes.

Fig. 4 is that expression is used for the figure that the optimal way to the branch light curve (spectral reflectance curve, reflectance curve) of the light-proofness film with anti-reflective function describes.

Fig. 5 is that expression is used for figure that the gray scale mask with semi-transparency film is described, (1) expression part vertical view; (2) expression fragmentary cross-sectional view.

Fig. 6 is that expression is used for figure that the gray scale mask with the fine light-shielding pattern below the imaging limit is described, (1) expression part vertical view; (2) expression fragmentary cross-sectional view.

Fig. 7 is the figure as a result that expression is analyzed the composition of light-proofness film on the film depth direction of embodiment 4 by Auger electron spectroscopy.

Symbol description

1 light shielding part

2 see through portion

3 gray scale portions

The fine light-shielding pattern of 3a

The fine portion that sees through of 3b

3a` semi-transparency film

Embodiment

Below, the present invention is described in detail.

The present invention should be used to make the mask base plate and the mask of FPD device, it is characterized in that, it is the light-proofness film that constitutes by lower layer part with shade function and upper layer part at least with anti-reflective function, be from the wavelength band territory from the i line to the g line at least of ultrahigh pressure mercury lamp radiation, the change width of cloth of face reflectivity is controlled in and is lower than 1% the interior film (constituting 1) of scope.

In the present invention, in order to make the light-proofness film that satisfies above-mentioned condition,, also need to confirm the adjustment of forming by to film except selecting to think to have the membrane material of the possibility (being suitable for satisfying above-mentioned condition) that satisfies above-mentioned condition; To create conditions, the selected and control of manufacturing installation etc.; Thus to membranous control, the material of light-proofness film etc., above-mentioned condition can be satisfied in the position of peak base, film formation etc.In addition, even identical membrane material, owing to the adjustment that film is formed; To create conditions, the selected and control of manufacturing installation etc.; Thus to membranous control, the material of light-proofness film etc., also there are the goods that satisfy above-mentioned condition and do not satisfy above-mentioned condition in the position of peak base (dividing light curve (spectral reflectance curve, reflectance curve) minimum reflectance part), the difference that film constitutes etc.

In the present invention, under aforesaid situation, described light-proofness film is to be made into optical design to be: from the wavelength band territory from the i line to the g line at least of ultrahigh pressure mercury lamp radiation, the change width of cloth of face reflectivity is in being lower than 1% scope, face reflectivity for i line, h line, g line is almost equal, is not subjected to the film of wavelength restriction.

In addition, in the present invention, the lower layer part with shade function is the high part of shade function, is most or all of parts of having given play to the shade function that is required.In addition, having the upper layer part of anti-reflective function, be formed on the lower layer part with shade function, is that the reflectivity of the lower layer part with shade function is descended, the part of performance anti-reflective function.

Should be used for making the mask base plate and the mask of FPD device in the present invention, preferred described light-proofness film is the film (constituting 2) that described face reflectivity is controlled in the wavelength coverage that becomes minimum minimum reflectance 380nm～430nm.

Its reason is, the face reflectivity becomes minimum minimum reflectance (promptly, the position of peak base) is controlled in the film of the wavelength coverage of 380nm～430nm, the displacement of the branch light curve that produces with respect to adjoint process change on direction up and down, spectral reflectance (reflectivity in each wavelength) can not produce big change, the having good uniformity of spectral reflectance (reflectivity in each wavelength).In addition, even under the situation of creating conditions in the film forming of light-proofness film (membrance casting condition) change, also seldom therefore cause spectral reflectance (reflectivity in each wavelength) to change, can produce mask base plate up to specification, that have good yield rate and mask.

The mask base plate and the mask that should be used for making the FPD device in the present invention, preferred described light-proofness film is made as: constitute by the lower layer part of the chromium carbide class with shade function (material type that comprises chromium and carbon) and upper layer part with nitrogen chromium oxide class (material type that contains chromium and oxygen and nitrogen) of anti-reflective function, described lower layer part and upper layer part by optical design for satisfying above-mentioned condition (formation 3).

Its reason is, compares with the film of other materials class, and the film of being made up of these material types (for example the film that is made of CrC light-proofness layer (lower layer part)/CrON antireflection film (upper layer part) etc.) is by the adjustment that film is formed; To create conditions, the selected and control of manufacturing installation etc.; Thus to membranous control, the material of light-proofness film etc., the position of peak base, film formation etc. are made the film that satisfies above-mentioned condition easily, and promptly the change width of cloth of face reflectivity is being lower than film in 1% the scope in the wavelength band territory of i line～g line.

Moreover, to compare with the film of other materials class, the film of being made up of these material types (for example the film that is made of CrC light-proofness layer (lower layer part)/CrON antireflection film (upper layer part) etc.) is by the adjustment that film is formed; To create conditions, the selected and control of manufacturing installation etc.; Thus to membranous control, the material of light-proofness film etc., the position of peak base, film formation etc., be formed in easily in the wavelength band territory of wavelength 350nm～450nm, the change width of cloth of face reflectivity is controlled in and is lower than 1% the interior film of scope, thus, and with respect to the branch light curve displacement of direction to the left and right of adjoint process change, spectral reflectance (reflectivity in each wavelength) can not produce big change, the having good uniformity of spectral reflectance (reflectivity in each wavelength).Relative therewith, for example in the wavelength band territory that comprises i line～g line, even the amplitude of fluctuation of face reflectivity is little, in the wavelength band territory at its two ends, divide light curve (spectral reflectance curve, reflectance curve) when sharply rising, can think and only direction offset slightly to the left and right of branch light curve (spectral reflectance curve) will exceed specification requirement.

In addition, the film of being made up of these material types (for example the film that is made of CrC light-proofness layer (lower layer part)/CrON antireflection film (upper layer part) etc.) is compared with the film of other materials class, by the adjustment that film is formed; To create conditions, the selected and control of manufacturing installation etc.; Thus to membranous control, the material of light-proofness film etc., the position of peak base, film formation etc., shown in Fig. 2 A line, C line, can make the approximate centre in wavelength band territory of the corresponding i line in peak base～g line of face reflectivity, be near 400 ± 10nm the h line (405nm), thus, displacement with respect to the direction up and down of the branch light curve of adjoint process change, spectral reflectance (reflectivity in each wavelength) can not produce big change, can obtain the film that has good uniformity of spectral reflectance (reflectivity in each wavelength).

The mask base plate and the mask that should be used for making the FPD device in the present invention, preferred described light-proofness film is made as: by the basalis of chromium nitride class (material type that comprises chromium and nitrogen), lower layer part with the chromium carbide class with shade function (material type that comprises chromium and carbon), and the upper layer part with nitrogen chromium oxide class (material type that comprises chromium and oxygen and nitrogen) of anti-reflective function constitutes, described basalis, lower layer part and upper layer part by optical design for satisfying above-mentioned condition (formation 4).

Its reason is, in the film that constitutes by these materials (for example the film that constitutes by CrN basalis/CrC light-proofness layer (lower layer part)/CrON anti-reflection layer (upper layer part) etc.), by by comprising building device in line style and forming continuously of basalis, the branch light curve of face reflectivity produces delicate variation, thus, shown in the A line of Fig. 2, the peak base of (1) face reflectivity is positioned at the approximate centre in the wavelength band territory of i line～g line, promptly near the h line (405nm); (2) can obtain with the peak base is the branch light curve of roughly symmetrical face reflectivity at center; (3) and the wavelength band territory from the i line to the g line, the maximal value that can obtain the face reflectivity is the branch light curve below 12%.Thus, can obtain the branch light curve displacement of left and right directions up and down with respect to the adjoint process change, the change of spectral reflectance (reflectivity in each wavelength) is littler, the better film of homogeneity of spectral reflectance (reflectivity in each wavelength).In addition, passing through in film line style sputter equipment continuous film forming, that constitute by CrN basalis/CrC light-proofness layer (lower layer part)/CrON anti-reflection layer (upper layer part), can on the surface of each film, not form oxide layer, therefore easily optical characteristics (reflectivity etc.) be carried out strict control.

In the present invention, as ultrahigh pressure mercury lamp, for example can enumerate example, but the present invention is not limited thereto with characteristic shown in Figure 1.

In addition, as light-transmitting substrate, can enumerate the substrate of synthetic quartz, soda-lime glass, alkali-free glass etc.

In the present invention, as the mask base plate and the mask that are used to make the FPD device, can enumerate the mask base plate and the mask that are used to make FPD devices such as LCD (LCD), plasma scope, organic EL (electroluminescence) display.

Here, at the mask that is used for making LCD, comprise and make the required all masks of LCD, for example: comprise the mask that is used to form TFT (thin film transistor (TFT)), particularly TFT channel part and contact hole portion, low-temperature poly-silicon TFT, color filter, reflecting plate (Black matrix) etc.At the mask of the display device that is used for making other, comprise all required masks such as making organic EL (Electroluminescence) display, plasma scope.

In addition, in this mask base plate of the present invention and mask, by light-transmitting substrate, with be formed on this light-transmitting substrate, lower layer part with shade function, and be formed on this lower layer part, mask base plate with upper layer part formation of anti-reflective function, described lower layer part and described upper layer part formed by pattern be treated as photomask after, when making device, by comprising the exposure light of a plurality of wavelength, be exposed the mask base plate that the photomask of processing is used, it is characterized in that, the reflectance curve of mask base plate is constituted as with respect to light wavelength, is protruding curve down, the minimal reflection of described reflectance curve is commanded troops, and becomes in the wavelength band territory of corresponding described exposure light (to constitute 5).

Here, minimal reflection commands troops to be meant in the reflectance curve of mask base plate, the field till from the reflectivity (minimum reflectance) of minimum to 0.5% high reflectance.Command troops to become in the wavelength band territory of corresponding exposure light by the minimal reflection that makes this reflectance curve, even under the situation of creating conditions in the film forming of light-proofness film (membrance casting condition) change, spectral reflectance (reflectivity in each wavelength) with low uncertainty can produce mask base plate and mask up to specification with good yield rate.In addition, the film of so being controlled, with respect to the displacement of the direction up and down of the reflectance curve of adjoint process change, spectral reflectance (reflectivity in each wavelength) seldom produces big change, the having good uniformity of spectral reflectance (reflectivity in each wavelength).Because the reflectivity of mask base plate, mask surface is controlled in the wide wavelength band territory, when therefore making device, suitable pattern can occur and form the phenomenon of being obstructed by exposure-processed.

In addition, mask base plate of the present invention and mask, preferably have in the wavelength band territory more than i line wavelength (365nm), below the g line wavelength (436nm), reflectivity becomes minimum formation (constituting 6), more excellent in having in fact in h line wavelength (405nm), the reflectivity of mask base plate becomes minimum formation (constituting 7).Here h line wavelength is meant the wavelength band territory of 405nm ± 10nm in fact.

In addition, mask base plate of the present invention and mask owing to be no more than 13% (constituting 8) with respect to the maximum reflectivity in the wavelength band territory of exposure light, can carry out more suitable pattern and form when make device by exposure-processed.Be below 12% with respect to the maximum reflectivity the wavelength band territory of exposure light (specifically, for from i line wavelength to g line wavelength) preferably, more excellent is below 11.5%, and more excellent is below 11%.

In addition, mask base plate of the present invention and mask can preferably wait mask base plate, the photomask (constituting 9) of the exposure machine of times exposure-processed as correspondence.

In addition, mask base plate of the present invention and mask, by constituting in lower layer part that has shade function on the light-transmitting substrate and the upper layer part that above this lower layer part, has an anti-reflective function, the composition of preferred described lower layer part and described upper layer part adjacent part has from the composition of described lower layer part towards the continuity migration of described upper layer part.

In addition, the more excellent major component that constitutes described upper layer part and described lower layer part is made as identical element, has to make the content composition of migration inclination continuously on film thickness direction of adding element.For example, as the element of described major component, can be made as metallic element.As metallic element, can enumerate the migration metal of chromium or tantalum etc., but be preferably chromium.In addition,, element be can enumerate, nitrogen or oxygen wherein are preferably with anti-reflective function as adding element.As optimal way, for example has following preferred formation: be that major component constitutes lower layer part with chromium, constitute upper layer part with the material that comprises chromium and nitrogen and/or oxygen, on the boundary member of described lower layer part and described upper layer part, the content of nitrogen and/or oxygen increases continuously on film thickness direction.

In addition, the present invention this mask base plate and mask are preferably used as mask base plate, mask that corresponding light optics class is constituted as the exposure device of catoptrics formula.

In addition, the present invention this mask base plate and mask are preferably used as the above large-scale mask of 330mm * 450mm rectangle, and to large-scale mask base plate that should mask.As the purposes of this large-scale mask, can enumerate the mask that is used to make display device, for example the FPD device is made with photomask etc.

In addition, preferred the present invention is the mask base plate of corresponding grey scale mask.

Be used to make the photomask of FPD device of the present invention, it is characterized in that, can adopt the mask base plate that is used to make this FPD device of the invention described above to make (constitute 10, constitute 11).

Below, the present invention will be described in more detail according to embodiment.

(embodiment 1)

In large-size glass substrate (synthetic quartz (QZ) system, on the thick 10mm, size 850mm * 1200mm), use large-scale online sputter equipment, carry out the film forming of light-proofness film, this light-proofness film is made of basalis, the lower layer part with shade function, the upper layer part with anti-reflective function.During film forming, in each space (sputtering chamber) in being configured in large-scale online sputter equipment continuously, dispose the Cr target respectively, carry out continuous film forming, at first with Ar gas and N ₂Gas is as sputter gas, and the CrN layer of film forming 150 dusts (is the basalis of purpose with the adhesion that strengthens for glass) is secondly with Ar gas and CH ₄Gas is as sputter gas, the CrC layer of film forming 650 dusts (lower layer part) with shade function, then with Ar gas and NO gas as sputter gas, the CrON film of film forming 250 dusts (upper layer part with anti-reflective function) is made the mask base plate.In addition, each film is respectively and forms the inclination film.In addition, because the N that uses when film forming CrN basalis and CrON layer (upper layer part) with anti-reflective function ₂The effect of gas and NO gas contains N (nitrogen) in the CrC layer (lower layer part with shade function), contains Cr and N in all of above-mentioned basalis, CrC layer (lower layer part with shade function), CrON layer (upper layer part with anti-reflective function).

The branch light curve of above-mentioned test portion (spectral reflectance curve, reflectance curve) is shown in the A of Fig. 2.In addition, by the spectral reflectance meter spectral reflectance is measured.

In branch light curve shown in Figure 2 (spectral reflectance curve, reflectance curve) A, from the wavelength band territory from the i line to the g line at least of ultrahigh pressure mercury lamp radiation, the change width of cloth of face reflectivity is in being lower than 1% (0.8%) scope.Specifically, the change width of cloth that is exactly the face reflectivity is 0.8%, is controlled to be lower than in 1% the scope.In addition, the maximal value of the face reflectivity in this wavelength band territory is below 12.0%.

In addition, in branch light curve shown in Figure 2 (spectral reflectance curve, reflectance curve) A, in the wavelength band territory of wavelength 350nm ~ 450nm, the change width of cloth of face reflectivity is in being lower than 2% (1.8%) scope.Specifically, the change width of cloth that is exactly the face reflectivity is 1.8%, is controlled to be lower than in 2% the scope.In addition, the maximal value of the face reflectivity in this wavelength band territory is 12.8%.

In face (impartial 9 places) have carried out same investigation for many (between substrates: 100), all confirm in the scope of the amplitude of fluctuation of above-mentioned face reflectivity.

(embodiment 2)

In large-size glass substrate (synthetic quartz (QZ) system, on the thick 10mm, size 850mm * 1200mm), use large-scale online sputter equipment, carry out the film forming of light-proofness film, this light-proofness film is made of basalis, the lower layer part with shade function, the upper layer part with anti-reflective function.During film forming, in each space (sputtering chamber) in being configured in large-scale online sputter equipment continuously, dispose the Cr target respectively, carry out continuous film forming, at first with Ar gas and N ₂Gas is as sputter gas, and the CrN layer of film forming 150 dusts (is the basalis of purpose with the adhesion that strengthens for glass) is secondly with Ar gas and CH ₄Gas and He gas is as sputter gas, the CrC layer of film forming 630 dusts (lower layer part) with shade function, then with Ar gas and NO gas as sputter gas, the CrON film of film forming 250 dusts (upper layer part with anti-reflective function) is made the mask base plate.In addition, each film is respectively and forms the inclination film.In addition, because the N that uses when film forming CrN basalis and CrON layer (upper layer part) with anti-reflective function ₂The effect of gas and NO gas contains N (nitrogen) in the CrC layer (lower layer part with shade function), contains Cr and N in all of above-mentioned basalis, CrC layer (lower layer part with shade function), CrON layer (upper layer part with anti-reflective function).In addition, CrC layer (lower layer part with shade function) is the layer that contains He.

The branch light curve of above-mentioned test portion (spectral reflectance curve, reflectance curve) is shown in the B of Fig. 2.In addition, by the spectral reflectance meter spectral reflectance is measured.

In branch light curve shown in Figure 2 (spectral reflectance curve, reflectance curve) B, from the wavelength band territory from the i line to the g line at least of ultrahigh pressure mercury lamp radiation, the change width of cloth of face reflectivity is in being lower than 1% (0.8%) scope.Specifically, the change width of cloth that is exactly the face reflectivity is 0.8%, is controlled to be lower than in 1% the scope.In addition, the maximal value of the face reflectivity in this wavelength band territory is 1 2.7%.

In addition, in branch light curve shown in Figure 2 (spectral reflectance curve, reflectance curve) B, in the wavelength band territory of wavelength 350nm～450nm, the change width of cloth of face reflectivity is in being lower than 2% (1.3%) scope.Specifically, the change width of cloth that is exactly the face reflectivity is 1.3%, is controlled to be lower than in 2% the scope.In addition, the maximal value of the face reflectivity in this wavelength band territory is 13.2%.

(embodiment 3)

In large-size glass substrate (synthetic quartz (QZ) system, on the thick 10mm, size 850mm * 1200mm), use large-scale online sputter equipment, carry out the film forming of light-proofness film, this light-proofness film is made of basalis, the lower layer part with shade function, the upper layer part with anti-reflective function.During film forming, in each space (sputtering chamber) in being configured in large-scale online sputter equipment continuously, dispose the Cr target respectively, carry out continuous film forming, at first with Ar gas and CH ₄Gas is as sputter gas, the CrC layer of film forming 500 dusts (lower layer part) with shade function, secondly with Ar gas and NO gas as sputter gas, the CrON film of film forming 450 dusts (upper layer part with anti-reflective function) is made the mask base plate.In addition, each film is respectively and forms the inclination film.In addition, because the effect of the NO gas that uses during film forming CrON layer (upper layer part) with anti-reflective function, contain N (nitrogen) in the CrC layer (lower layer part), contain Cr and N among both of above-mentioned CrC layer (lower layer part), CrON layer (upper layer part) with anti-reflective function with shade function with shade function.

The branch light curve of above-mentioned test portion (spectral reflectance curve, reflectance curve) is shown in the C of Fig. 2.In addition, by the spectral reflectance meter spectral reflectance is measured.

In branch light curve shown in Figure 2 (spectral reflectance curve, reflectance curve) C, from the wavelength band territory from the i line to the g line at least of ultrahigh pressure mercury lamp radiation, the change width of cloth of face reflectivity is in being lower than 1% (0.3%) scope.Specifically, the change width of cloth that is exactly the face reflectivity is 0.3%, is controlled to be lower than in 1% the scope.In addition, the maximal value of the face reflectivity in this wavelength band territory is 12.2%.

In addition, in branch light curve shown in Figure 2 (spectral reflectance curve, reflectance curve) C, in the wavelength band territory of wavelength 350nm ~ 450nm, the change width of cloth of face reflectivity is in being lower than 2% (0.7%) scope.Specifically, the change width of cloth that is exactly the face reflectivity is 0.7%, is controlled to be lower than in 2% the scope.In addition, the maximal value of the face reflectivity in this wavelength band territory is 12.6%.

(comparative example 1)

(synthetic quartz (QZ) system on the thick 10mm, size 850mm * 1200mm), is used large-scale online sputter equipment, carries out the film forming of basilar memebrane, light-proofness film and antireflection film at large-size glass substrate.During film forming, in each space (sputtering chamber) in being configured in large-scale online sputter equipment continuously, dispose the Cr target respectively, carry out continuous film forming, at first with Ar gas and CO ₂Gas is as sputter gas, the CrO film of film forming 300 dusts (glass antireflection film), secondly with Ar gas as sputter gas, the Cr film of film forming 900 dusts (light-proofness film), then, with Ar gas and CO ₂Gas is as sputter gas, and the CrO film of film forming 300 dusts (face antireflection film) is made the mask base plate.

The branch light curve of above-mentioned test portion (spectral reflectance curve, reflectance curve) is shown in the D of Fig. 2.In addition, by the spectral reflectance meter spectral reflectance is measured.

In branch light curve shown in Figure 2 (spectral reflectance curve, reflectance curve) D, from the wavelength band territory from the i line to the g line at least of ultrahigh pressure mercury lamp radiation, the change width of cloth of face reflectivity surpasses 2% (2.3%).Specifically, the change width of cloth that is exactly the face reflectivity is 2.3%, has surpassed 2%.In addition, the maximal value of the face reflectivity in this wavelength band territory is 13.6%.

In addition, in branch light curve shown in Figure 2 (spectral reflectance curve, reflectance curve) D, in the wavelength band territory of wavelength 350nm ~ 450nm, the change width of cloth of face reflectivity surpasses 3% (3.3%).Specifically, the change width of cloth that is exactly the face reflectivity is 3.3%, has surpassed 3%.In addition, the maximal value of the face reflectivity in this wavelength band territory is 14.57%.

In face (impartial 9 places) have carried out same investigation for many (between substrates: 100), found that, the change of slightly process produces displacement about all can making branch light curve (spectral reflectance curve, reflectance curve) C up and down, thereby causes the significantly change of face reflectivity.

(embodiment 4)

In large-size glass substrate (synthetic quartz (QZ) system, on the thick 10mm, size 850mm * 1200mm), use large-scale online sputter equipment, carry out the film forming of light-proofness film, this light-proofness film is made of basilar memebrane, the lower layer part with shade function, the upper layer part with anti-reflective function.During film forming, in each space (sputtering chamber) in being configured in large-scale online sputter equipment continuously, dispose the Cr target respectively, carry out continuous film forming, at first with Ar and N ₂Gas is as sputter gas, and the CrN layer of film forming 150 dusts (is the basalis of purpose with the adhesion that strengthens for glass) is secondly with Ar and CH4 gas and N ₂Gas is as sputter gas, the CrCN layer of film forming 620 dusts (lower layer part) with shade function, then with Ar gas and NO gas as sputter gas, the CrON film of film forming 230 dusts (upper layer part with anti-reflective function) is made the mask base plate.For the film of making, the composition on the film thickness direction of light-proofness film is analyzed by electronic spectroscopy.Its result as shown in Figure 7.As Fig. 7, on the border of the CrON of the CrCN of lower layer part layer and upper layer part layer, on the surface direction of photomask, the inclination film of the composition that formation oxygen and nitrogen increase continuously.In addition, the basalis that lies across, lower layer part, upper layer part constitute chromium, carbon, oxygen, the nitrogen of light-proofness film, are formed on the inclination film of the composition that has moved continuously on the film thickness direction.Moreover, be the film that in basalis, lower layer part, upper layer part whole, contains chromium and nitrogen.

By the spectral reflectance meter reflectivity on the film surface of this light-proofness film is measured, found that from the wavelength band territory from the i line to the g line at least of ultrahigh pressure mercury lamp (extra-high-pressure mercury vapour lamp) radiation, the change width of cloth of face reflectivity is 0.8%, in being lower than 1% scope.In addition, same with the above embodiments 1 to 3, reflectivity becomes minimum minimal reflection commands troops, roughly near h line (405nm).In addition, the maximal value of the face reflectivity in this wavelength band territory is below 11.0%.Moreover in the wavelength band territory of wavelength 350nm～450nm, the change width of cloth of face reflectivity is 1.5%, in being lower than 2% scope.In addition, the maximal value of the face reflectivity in this wavelength band territory is 11.7%.

(making of mask)

The mask base plate that employing is made from the foregoing description 1 to embodiment 4 and comparative example 1, the pattern that carries out the light-proofness film forms, and makes the large-scale mask of FPD.

Found that, compare, use under the situation of the film of embodiment 1 to embodiment 4, be of value to and make mask realize high-qualityization and improve yield rate etc. with the situation of the film that uses comparative example 1.

More than, describe the present invention by preferred embodiment, but the present invention is not limited to the foregoing description.

Claims

1. mask base plate that is used to make the FPD device, it has the light-proofness film on light-transmitting substrate, and this light-proofness film is made of lower layer part with shade function and upper layer part with anti-reflective function at least, and described mask base plate is characterised in that,

2. the mask base plate that is used to make the FPD device according to claim 1 is characterized in that, described light-proofness film is that described face reflectivity is controlled in that to become minimum minimum reflectance be the film of the wavelength coverage of 380nm～430nm.

3. the mask base plate that is used to make the FPD device according to claim 1 and 2, it is characterized in that, described light-proofness film is made of with the upper layer part with nitrogen chromium oxide class of anti-reflective function the lower layer part of the chromium carbide class with shade function, and described lower layer part and upper layer part are made as by optical design and satisfy above-mentioned important document.

4. the mask base plate that is used to make the FPD device according to claim 1 and 2, it is characterized in that, described light-proofness film is by the basalis of chromium nitride class and have the lower layer part of chromium carbide class of shade function and the upper layer part with nitrogen chromium oxide class of anti-reflective function constitutes, and described basalis, lower layer part and upper layer part are made as by optical design and satisfy above-mentioned important document.

5. a mask base plate is characterized in that, by light-transmitting substrate be formed at the lower layer part on this substrate and be formed on the upper layer part that has anti-reflective function on this lower layer part and be laminated with shade function,

Described mask base plate be described lower layer part and described upper layer part formed by pattern be treated as photomask after, when making device, the mask base plate that the photomask of the exposure light exposure-processed of involved a plurality of wavelength is used,

The reflectance curve of described mask base plate constitutes with respect to light wavelength and is protruding curve downwards, and the minimal reflection of described reflectance curve commands troops to become in the wavelength band territory corresponding to described exposure light.

6. mask base plate according to claim 5 is characterized in that, the above g line of i line wavelength wavelength with interior wavelength band territory in, reflectivity becomes minimum.

7. according to claim 5 or 6 described mask base plates, it is characterized in that reflectivity becomes minimum in h line wavelength in fact.

8. according to each described mask base plate in the claim 5～7, it is characterized in that, be no more than 13% corresponding to the maximum reflectivity in the wavelength band territory of described exposure light.

9. according to each described mask base plate in the claim 5～8, it is characterized in that, is the mask base plate of using corresponding to the photomask of the exposure machine that waits times exposure-processed.

10. a photomask that is used to make the FPD device is characterized in that, each described mask base plate is made in the employing claim 1～4.

11. a photomask is characterized in that, each described mask base plate is made in the employing claim 5～9.