CN101650527B - Gray tone mask blank, gray tone mask and forming method of product machining identification or product information identification - Google Patents

Gray tone mask blank, gray tone mask and forming method of product machining identification or product information identification Download PDF

Info

Publication number
CN101650527B
CN101650527B CN 200910160207 CN200910160207A CN101650527B CN 101650527 B CN101650527 B CN 101650527B CN 200910160207 CN200910160207 CN 200910160207 CN 200910160207 A CN200910160207 A CN 200910160207A CN 101650527 B CN101650527 B CN 101650527B
Authority
CN
China
Prior art keywords
semi
mentioned
light
photomask
wavelength
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN 200910160207
Other languages
Chinese (zh)
Other versions
CN101650527A (en
Inventor
深谷创一
金子英雄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Chemical Co Ltd
Original Assignee
Shin Etsu Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2008209128A external-priority patent/JP4831368B2/en
Application filed by Shin Etsu Chemical Co Ltd filed Critical Shin Etsu Chemical Co Ltd
Publication of CN101650527A publication Critical patent/CN101650527A/en
Application granted granted Critical
Publication of CN101650527B publication Critical patent/CN101650527B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

Gray tone mask blank has a semitransmitting membrane and a lightproof membrane formed by membranes with mutually different etching characteristics. The reflectivity of the semitransmitting membrane and the lightproof membrane are both smaller than or equal to 30% under the wavelength of exposure light, the reflectivity difference of the semitransmitting membrane and the lightproof membrane under a specified wavelength of the wavelength side longer than the wavelength of the exposure light is formed and is made to be larger than the reflectivity difference under the wavelength of the exposure light. And when the semitransmitting membrane and the lightproof membrane are made into the gray tone mask, the semitransmitting membrane and the lightproof membrane can be identified based on the their reflectivity difference, by irradiation of the light with the specified wavelength to the semitransmitting membrane and the lightproof membrane from any side of the positive and negative sides of the gray tone mask. Even when the product machining identification and product information identification are formed by the semitransmitting membrane and the lightproof membrane, the identification can be formed by removing the lithographic printing process of one side of either the semitransmitting membrane or the lightproof membrane, and the identification that can be read by reflection light and can utilize the light with the prescribed reading wavelength is formed.

Description

The formation method of gray mask base, gray mask and product machining identification or product information sign
Technical field
The present invention relates to become the raw-material photo blanks (gray mask base (gray tone mask blank)) of the photomask (gray mask) of making etc. for SIC (semiconductor integrated circuit) etc., particularly become raw-material gray mask base and the gray mask with suitable gray mask as FPD (flat-panel monitor), and the formation method of the product machining identification that in gray mask, forms or product information sign.
Background technology
In recent years, in the manufacturing of TFT liquid crystal indicator, used gray mask in order to simplify manufacturing process.Common photomask is made of transmittance section and light shielding part, the exposure light intensity that sees through mask is actually shading and 2 values of printing opacity, gray mask is comprised of transmittance section, semi light transmitting part and light shielding part, change becomes shading, semi-transparent and 3 values of printing opacity from the exposure light intensity that various piece sees through.Having used the exposure of gray mask, is to use gray mask to utilize 1 photomask to carry out the exposure of the operation that common 2 photomasks bear.
As one of manufacture method of such gray mask, the use chromium compound has been proposed as photomask, semi light transmitting part reduces thickness by partially-etched photomask, with the technical scheme (Unexamined Patent 7-49410 communique) of the transmissivity that obtains stipulating.
But, so partly carrying out in the etching method, owing to being difficult to semi light transmitting part in comprehensively equably etching of photomask, therefore proposed to make 2 layers of structure of photomask and semi-transparent film, use the method for the photo blanks that has utilized respectively alternative etched material.As such method, following methods is disclosed: use Cr in photomask, in semi-transparent film, use MoSi, having used chlorine in the patterning of the Cr of photomask is the dry ecthing of gas or the wet etching that has used the mixed solution of cerous nitrate and perchloric acid, and using fluorine in the etching of MoSi is gas (JP 2005-37933 communique).
On the other hand, photomask is at the outside of the part that forms pattern, the mask information marks such as the ID of the masks such as the telltale mark of aligned position and bar code, numeral, letter and kind when sometimes being formed for exposing.In addition, when making gray mask, in order to form respectively the pattern of semi light transmitting part and light shielding part, in lithography (lithography), to carry out 2 exposures, at this moment, for aligned position needs telltale mark sometimes in advance.
Summary of the invention
When photomask is used for exposure, in order to prevent that light shielding part will be selected the low material of exposure light reflectivity from the ghost image pattern of the reflected light generation of photomask.On the other hand, utilize reflected light to read in the situation of telltale mark and mask information mark, need to have part with the film that has formed mark and poor without the reflectivity of the part of this film.In the situation of the photomask of the existing shading that is comprised of light shielding part and transmittance section and 2 values of printing opacity, be photomask owing to having formed the film of mark, the part that does not have photomask is transparency carrier, so the difference of reflectivity is enough large, fully certification mark.
But, in the photo blanks of above-mentioned 2 layers membrane structure with the different semi-transparent film of etching characteristic and photomask, forming above-mentioned mark profit uses the same method in the situation about reading, because the etching characteristic of each film is different, in order to form the large mark of reflection differences, in telltale mark and mask information mark part, because the semi-transparent film of etching and photomask are so that the transmittance section is transparency carrier shows out, also need the etching in 2 stages, so complicated.
On the other hand, attempted only the photomask etching being removed to form mark with the existing photo blanks with semi-transparent film and photomask, but, only pay attention to the inhibitory reflex rate and double light-transmissive film and photomask carry out material when selecting, semi-transparent film and photomask are in the provision wavelengths of comparing long wavelength side with the exposure light of photomask (for example, the inspection wavelength of photo blanks and photomask) reflection differences under diminishes, in this case, form above-mentioned mark even only photomask is partly removed, can not read mark.
In addition, for the gray mask with semi-transparent film and photomask, although the method for adding light element in order to reduce reflectivity is arranged, but when adding light element reduction reflectivity, because the light-proofness of the per unit thickness of film descends, so have the problem of necessary thickening thickness for the reflectivity that fully reduces semi-transparent film.If thickness increases, the processability of film reduces.
In addition, semi-transparent film is owing to usually having the effect of Phase shift that makes exposure light, so during the thickness thickening, the migration quantitative change of phase place is large.When this Phase shift quantitative change is large, passed through respectively the interference of light of semi light transmitting part and transmittance section, on the border of semi light transmitting part and transmittance section because interference of light has the problem that forms the low part of transmissivity.
The present invention finishes for addressing the above problem, so that gray mask to be provided, become the raw-material gray mask base of such gray mask, and the product machining identification that forms at gray mask or the formation method of product information sign are the first purpose, in having the gray mask base of semi-transparent film and photomask, even if (formed the situation of mark with photomask take semi-transparent film as background in the situation that has formed product information signs such as the product machining identifications such as telltale mark and mask information mark etc. with semi-transparent film and photomask, perhaps formed the situation of mark with semi-transparent film take photomask as background) in, also can identify and read these signs.
In addition, the second purpose of the present invention is to be provided at the gray mask of guaranteeing transmissivity that semi light transmitting part is required and reflectivity under the thickness of not thickening semi light transmitting part and becomes its raw-material gray mask base.
The inventor is for solving repeatedly active research of above-mentioned problem, found that, as gray mask, it has the transmittance section, light shielding part and semi light transmitting part, light shielding part carries out shading with the degree that exposure is not contributed to exposure light, semi light transmitting part is for exposure light, have the transmissivity lower and higher than the transmissivity of light shielding part than the transmissivity of transmittance section, and has the transmissivity that exposure is contributed, semi light transmitting part and light shielding part are formed by the film with mutually different etching characteristic, semi light transmitting part and the light shielding part reflectivity under the exposure light wavelength is all less than or equal to 30%, be formed on than the semi light transmitting part under the provision wavelengths of the long wavelength side of light wavelength of exposing and the reflection differences of light shielding part, make it greater than the reflection differences under the exposure light wavelength, and semi light transmitting part and light shielding part be by from the either side of the pros and cons (surface and the back side) of the gray mask light to semi light transmitting part and light shielding part irradiation afore mentioned rules wavelength, can identify the product information signs such as the product machining identification such as telltale mark that gray mask that semi light transmitting part and light shielding part form can utilize both reflection differences to identify and read to form with semi light transmitting part and light shielding part and mask information mark etc. according to both reflection differences.
And find: such gray mask can be with the gray mask base as the starting material manufacturing, the photomask that this gray mask base is formed for forming the semi-transparent film of semi light transmitting part and is used to form light shielding part at transparency carrier, semi-transparent film and photomask are formed by the film with mutually different etching characteristic, semi-transparent film and the photomask reflectivity under the exposure light wavelength is all less than or equal to 30%, be formed on than the semi-transparent film under the provision wavelengths of the long wavelength side of light wavelength of exposing and the reflection differences of photomask, make it greater than the reflection differences under the exposure light wavelength, and form semi-transparent film and photomask so that when the gray mask base is made gray mask, by from the either side of the pros and cons of the gray mask light to semi light transmitting part and light shielding part irradiation afore mentioned rules wavelength, reflection differences according to both can be identified semi light transmitting part and light shielding part, by the semi-transparent film of etching and photomask, cover light shielding part or the semi light transmitting part take light shielding part as background of middle utilization take semi light transmitting part as background at the grey mode transfer and can form the product information signs such as the product machining identification such as telltale mark and mask information mark.
In addition, the inventor finds to have the transmittance section by making, with the degree that exposure is not contributed exposure light is carried out the light shielding part of shading and has the transmissivity lower and higher than the transmissivity of light shielding part than the transmissivity of transmittance section for exposure light, gray mask with semi light transmitting part of the transmissivity that exposure is contributed becomes following gray mask: by to possess semi-transparent film at transparency carrier, the first antireflection film and photomask as the antireflection film of the reflectivity of adjusting this semi-transparent film, from above-mentioned transparent substrate side with semi-transparent film, the first antireflection film, the order of photomask forms gray mask base that these films form as starting material, respectively with comprising semi-transparent film and as the first antireflection film of the antireflection film of adjusting semi-transparent film reflectivity but do not comprise the semi light transmitting part of photomask and comprise semi-transparent film, consist of semi light transmitting part and light shielding part as the first antireflection film of the antireflection film of adjusting semi-transparent film reflectivity and the light shielding part of photomask, under the thickness of not thickening semi light transmitting part, guarantee transmissivity and reflectivity that semi light transmitting part is required, in addition, by reducing thickness, can prevent because the transmissivity that the interference of light on the border of semi light transmitting part and transmittance section causes reduces, thereby finish the present invention.
That is, as the first embodiment that is used for realizing above-mentioned the first purpose, the invention provides the formation method of following gray mask base, gray mask and product machining identification or product information sign.
[1] gray mask base, it is the raw-material gray mask base that becomes gray mask, this gray mask has transmittance section, light shielding part and semi light transmitting part, above-mentioned light shielding part carries out shading with the degree that exposure is not contributed to exposure light, above-mentioned semi light transmitting part is for exposure light, have the transmissivity lower and higher than the transmissivity of above-mentioned light shielding part than the transmissivity of above-mentioned transmittance section, and have the transmissivity that exposure is contributed, it is characterized in that:
Be formed for forming the semi-transparent film and the photomask that is used to form above-mentioned light shielding part of above-mentioned semi light transmitting part at transparency carrier;
Above-mentioned semi-transparent film and photomask are formed by the film with mutually different etching characteristic;
Above-mentioned semi-transparent film and the photomask reflectivity under the exposure light wavelength is all less than or equal to 30%;
Be formed on than the above-mentioned semi-transparent film under the provision wavelengths of the long wavelength side of light wavelength of exposing and the reflection differences of photomask, make it greater than the reflection differences under the exposure light wavelength; And
Form above-mentioned semi-transparent film and photomask, so that when the gray mask base made gray mask, by from the either side of the pros and cons of the gray mask light to above-mentioned semi light transmitting part and light shielding part irradiation afore mentioned rules wavelength, can identify above-mentioned semi light transmitting part and light shielding part according to both reflection differences.
[2] [1] described gray mask base is characterized in that: the reflectivity of above-mentioned semi-transparent film and photomask, and from above-mentioned exposure light wavelength to above-mentioned provision wavelengths, a side increases, and the opposing party reduces.
[3] [1] described gray mask base, it is characterized in that: above-mentioned exposure light is the light of wavelength 436nm, 405nm or 365nm, perhaps contains the light of at least a kind of wavelength in the above-mentioned wavelength.
[4] [1] described gray mask base is characterized in that: the wavelength of afore mentioned rules is the wavelength more than or equal to 500nm.
[5] [1] described gray mask base is characterized in that: the wavelength of afore mentioned rules be defect inspection with or product machining identification or product information sign read the wavelength of usefulness.
[6] [1] described gray mask base, it is characterized in that, from the either side of the pros and cons of the gray mask light time to above-mentioned semi light transmitting part and light shielding part irradiation afore mentioned rules wavelength, above-mentioned light shielding part and the reflection differences of above-mentioned semi light transmitting part under the afore mentioned rules wavelength are more than or equal to 10%.
[7] [1] described gray mask base, it is characterized in that: above-mentioned photomask contains transition metal and silicon, and above-mentioned semi-transparent film contains chromium.
[8] [1] described gray mask base, it is characterized in that: above-mentioned photomask contains chromium, and above-mentioned semi-transparent film contains transition metal and silicon.
[9] [1] described gray mask base is characterized in that: above-mentioned gray mask base is FPD gray mask base.
[10] gray mask, this gray mask has transmittance section, light shielding part and semi light transmitting part, above-mentioned light shielding part carries out shading with the degree that exposure is not contributed to exposure light, above-mentioned semi light transmitting part has the transmissivity lower and higher than the transmissivity of above-mentioned light shielding part than the transmissivity of above-mentioned transmittance section for exposure light, and have the transmissivity that exposure is contributed, it is characterized in that:
Above-mentioned semi light transmitting part and light shielding part are formed by the film with mutually different etching characteristic;
Above-mentioned semi light transmitting part and the light shielding part reflectivity under the exposure light wavelength is all less than or equal to 30%;
Form above-mentioned semi light transmitting part and the light shielding part reflection differences under the provision wavelengths of the wavelength side longer than the exposure light wavelength, make it greater than the reflection differences under the exposure light wavelength; And
Form above-mentioned semi light transmitting part and light shielding part, so that by from the either side of the pros and cons of the gray mask light to above-mentioned semi light transmitting part and light shielding part irradiation afore mentioned rules wavelength, can identify above-mentioned semi light transmitting part and light shielding part according to both reflection differences;
Have the product machining identification or the product information sign that are formed by the above-mentioned light shielding part take above-mentioned semi light transmitting part as background or the above-mentioned semi light transmitting part take above-mentioned light shielding part as background.
[11] the formation method of product machining identification or product information sign, it is to have the transmittance section, the gray mask of light shielding part and semi light transmitting part forms the method that the product machining identification that formed by above-mentioned semi light transmitting part and light shielding part or product information identify, above-mentioned light shielding part carries out shading with the degree that exposure is not contributed to exposure light, above-mentioned semi light transmitting part is for exposure light, have the transmissivity lower and higher than the transmissivity of above-mentioned light shielding part than the transmissivity of above-mentioned transmittance section, and has the transmissivity that exposure is contributed, it is characterized in that, use following gray mask base:
Be formed for forming the semi-transparent film and the photomask that is used to form above-mentioned light shielding part of above-mentioned semi light transmitting part at transparency carrier,
Form above-mentioned semi-transparent film and photomask as the film with mutually different etching characteristic,
Above-mentioned semi-transparent film and photomask at the reflectivity of exposure under the light wavelength all less than or equal to 30%,
Be formed on than the above-mentioned semi-transparent film under the provision wavelengths of the long wavelength side of light wavelength of exposing and the reflection differences of photomask, make it greater than the reflection differences under the exposure light wavelength, and
Above-mentioned semi-transparent film and photomask have been formed so that when the gray mask base made gray mask, by from the either side of the pros and cons of the gray mask light to above-mentioned semi light transmitting part and light shielding part irradiation afore mentioned rules wavelength, can identify above-mentioned semi light transmitting part and light shielding part according to both reflection differences;
By the above-mentioned semi-transparent film of etching and photomask, utilize above-mentioned light shielding part or the above-mentioned semi light transmitting part take above-mentioned light shielding part as background, formation product machining identification or product information sign take above-mentioned semi light transmitting part as background.
In addition, the second embodiment as being used for realizing above-mentioned the second purpose the invention provides following gray mask base and gray mask.
[12] gray mask base, it is the raw-material gray mask base that becomes gray mask, above-mentioned gray mask has transmittance section, light shielding part and semi light transmitting part, above-mentioned light shielding part carries out shading with the degree that exposure is not contributed to exposure light, above-mentioned semi light transmitting part is for exposure light, have the transmissivity lower and higher than the transmissivity of above-mentioned light shielding part than the transmissivity of above-mentioned transmittance section, and have the transmissivity that exposure is contributed, it is characterized in that:
Possess semi-transparent film at transparency carrier, as the first antireflection film and the photomask of the antireflection film of the reflectivity of adjusting semi-transparent film, form these films from above-mentioned transparent substrate side according to the order of semi-transparent film, the first antireflection film, photomask and form.
[13] [12] described gray mask base, it is characterized in that: the etching characteristic of above-mentioned the first antireflection film and above-mentioned photomask is different.
[14] [13] described gray mask base, it is characterized in that: the etching characteristic of above-mentioned the first antireflection film and above-mentioned semi-transparent film is identical.
[15] [13] described gray mask base, it is characterized in that: the etching characteristic of above-mentioned the first antireflection film and above-mentioned semi-transparent film is different.
[16] [13] described gray mask base, it is characterized in that: above-mentioned the first antireflection film utilizes fluorine-containing etching gas that it is carried out dry ecthing, and chloride and etching gas oxygen are had tolerance; Above-mentioned photomask has tolerance to the dry ecthing that utilizes fluorine-containing etching gas, and with chloride and etching gas oxygen it is carried out etching.
[17] [13] described gray mask base, it is characterized in that: above-mentioned photomask utilizes fluorine-containing etching gas that it is carried out dry ecthing, and chloride and etching gas oxygen are had tolerance; Above-mentioned the first antireflection film has tolerance to the dry ecthing that utilizes fluorine-containing etching gas, and with chloride and etching gas oxygen it is carried out etching.
[18] gray mask, it has the transmittance section, light shielding part and semi light transmitting part, above-mentioned light shielding part carries out shading with the degree that exposure is not contributed to exposure light, above-mentioned semi light transmitting part has the transmissivity lower and higher than the transmissivity of above-mentioned light shielding part than the transmissivity of above-mentioned transmittance section for exposure light, and has the transmissivity that exposure is contributed, it is characterized in that: possess and comprise semi-transparent film and as the first antireflection film of the antireflection film of adjusting semi-transparent film reflectivity and do not comprise the semi light transmitting part of photomask, and comprise semi-transparent film, as the first antireflection film of the antireflection film of adjusting semi-transparent film reflectivity and the light shielding part of photomask.
First embodiment of the invention, because semi-transparent film (semi light transmitting part) is enough different with the reflectivity of photomask (light shielding part), even if form with semi-transparent film (semi light transmitting part) and photomask (light shielding part) in the situation of the product information signs such as the product machining identification such as telltale mark and mask information mark, also can form by the lithography operation of removing the side of any one in photomask or the semi-transparent film product machining identification and product information sign, can form the light that reads wavelength that can utilize regulation, product machining identification and the product information sign of utilizing reflected light to read.In addition, under the exposure light wavelength, owing to guaranteeing that the reflectivity of semi-transparent film (semi light transmitting part) and photomask (light shielding part) is enough low, therefore can reduce in exposing the ghost image from the reflection generation of mask pattern.
In addition, second embodiment of the invention, by form the antireflection film of the reflectivity of adjusting semi-transparent film at semi-transparent film, can reduce the reflectivity of the semi light transmitting part after pattern forms.
In addition, by making the antireflection film of adjusting semi-transparent film reflectivity different with the etching characteristic of the photomask that forms at the antireflection film of adjusting semi-transparent film reflectivity, not only make handling ease, and can improve transmissivity controlled of semi-transparent film.
Description of drawings
Fig. 1 is fit to the sectional view of a routine gray mask base of the first embodiment of the present invention for expression.
Fig. 2 is fit to the sectional view of a routine gray mask of the first embodiment of the present invention for expression.
Fig. 3 is at the reflectivity of the semi-transparent film of film forming on the quartz base plate and photomask and the coordinate diagram of the transmissivity when having formed successively these films on quartz base plate among the expression embodiment 1.
Fig. 4 is at the reflectivity of the semi-transparent film of film forming on the quartz base plate and photomask and the coordinate diagram of the transmissivity when having formed successively these films on quartz base plate among the expression embodiment 2.
Fig. 5 is fit to the sectional view of a routine gray mask base of the second embodiment of the present invention for expression.
Fig. 6 is fit to the sectional view of a routine gray mask of the second embodiment of the present invention for expression.
Embodiment
Below the present invention is illustrated in greater detail.
[the first embodiment]
At first, the suitable object lesson as the first embodiment of the present invention is described.
Gray mask base of the present invention has semi-transparent film and photomask at transparency carriers such as quartz base plates, for example as shown in Figure 1, forms them from transparency carrier 1 side according to the order of semi-transparent film 2, photomask 3.These semi-transparent films 2 and photomask 3 are respectively to be used to form the semi light transmitting part of gray mask and the film of light shielding part, after making gray mask with such gray mask base as starting material, semi-transparent film 2 and photomask 3 become semi light transmitting part 21, the light shielding part 31 of gray mask as shown in Figure 2, the part of in addition, both being removed becomes transmittance section 11.The product information signs 4 such as the product machining identifications such as in addition, in the gray mask of the present invention, utilization take the transmittance section as light shielding part or the semi light transmitting part take light shielding part as background of background, the formation telltale mark or mask information mark.
Gray mask of the present invention has transmittance section, semi light transmitting part and light shielding part.The transmittance section is the part exposed of transparency carrier and have the transmissivity that exposure is contributed normally.In addition, light shielding part has the effect of exposure light being carried out shading with the degree that exposure is not contributed.On the other hand, semi light transmitting part has the transmissivity lower and higher than the transmissivity of light shielding part than the transmissivity of transmittance section, and has the transmissivity that exposure is contributed with respect to exposure light.The semi-transparent film that forms at the gray mask base in addition and photomask are too, photomask has the effect of exposure light being carried out shading with the degree that exposure is not contributed, semi-transparent film is with respect to exposure light, have the transmissivity lower and higher than the transmissivity of photomask than the transmissivity of transparency carrier, and have the transmissivity that exposure is contributed.
Semi-transparent film and the photomask of gray mask base of the present invention are formed by the film with mutually different etching characteristic, become the material that can distinguish selective etch.In addition, the semi light transmitting part of gray mask and light shielding part are formed by the film with mutually different etching characteristic.
For the photo blanks (gray mask base) of the gray tone type of the present invention that is consisted of by the different semi-transparent film of etching characteristic and photomask, by comprising the lithography operation that is used to form semi light transmitting part of following operation:
(1-1) the formation operation of the resist pattern of the part of protection formation semi light transmitting part,
(1-2) do not remove operation with half etching that sees through film of the part of resist protection, and
(1-3) strip operation of resist film and the lithography operation that is used to form light shielding part that comprises following operation:
(2-1) the formation operation of the resist pattern of the part of protection formation light shielding part,
(2-2) do not remove operation with the etching of the photomask of the part of resist protection, and
(2-3) average separately 1 time the known lithography operation of the strip operation of resist film, the pattern of formation semi light transmitting part and light shielding part can be made gray tone type photomask (gray mask).In addition, because semi-transparent film and photomask are alternative etched material respectively, therefore by simple etching operation, can form and have such as the shape that designs and light shielding part, the semi light transmitting part of thickness.
The semi light transmitting part and the light shielding part that form like this, in situation about using as gray mask, form the ghost image pattern for the light that exposes multipath reflection does not occur between mask and substrate, need to reduce both reflectivity under exposure light, require less than or equal to 30% particularly.Therefore, aspect the transmissivity of needs, semi-transparent film (semi light transmitting part) and the photomask (light shielding part) of part are for the material of reflection of light rate less than or equal to 30% that expose separately to be used in formation.
Semi-transparent film is when using as gray mask, having with the exposure light by semi light transmitting part makes the degree of the insufficient sensitization of resist film make the film of the transmissivity of optical attenuation, can be that monofilm can also be multilayer film, it can also be the film that in composition, has gradient, whole as semi-transparent film, transmissivity with centre of transmittance section and light shielding part, namely, transmissivity than the transmittance section is low, than the transmissivity of the transmissivity high (transmissivity than transparency carrier is low, and is higher than the transmissivity of photomask) of light shielding part.Particularly, preferred about 20～70% transmissivity for example.
As the material of semi-transparent film, for example, can use transition metal, contain the silicon of transition metal or in silicon, contain as required the material of the light elements such as aerobic, nitrogen, carbon, must be and photomask between alternative etched material.
Preferred material as semi-transparent film, particularly, can enumerate chromium, tantalum, molybdenum, tungsten, the transistion metal compounds (particularly not siliceous transistion metal compound) such as chromium compound, tantalum compound, molybdenum compound, tungsten compound, contain silicon compound, silicon compound (silicon compound that does not particularly contain transition metal) of the transition metal more than a kind that is selected from titanium, vanadium, cobalt, nickel, zirconium, niobium, molybdenum, hafnium, tantalum and tungsten etc., can particularly preferably use easy etching and processing chromium, chromium compound, contain the silicon compound of molybdenum, perhaps silicon compound.
The transmissivity of semi-transparent film and the control of reflectivity are decided by material and thickness, use in the situation of chromium compound, preferably contain chromium and are selected from the chromium compound more than a kind in oxygen, nitrogen and the carbon (particularly not siliceous chromium compound).Use the material that ratio is preferably following ranges that contains of each element: chromium is for more than or equal to 30 atom % and less than 100 atom %, is 30 atom %～70 atom % especially, especially is 35 atom %～60 atom %; Oxygen is 0 atom %～60 atom %, is 10 atom %～60 atom % especially; Nitrogen is 0 atom %～50 atom %, is 3 atom %～30 atom % especially; Carbon is 0 atom %～20 atom %, is greater than 0 atom % and less than or equal to 5 atom % especially, the film that can obtain having the object penetrating rate by suitable adjustment thickness.In addition, in the too high situation of reflectivity, generally increase thickness by improving the containing ratio of light element, can form the film that has the object penetrating rate and have the reflectivity of requirement.
On the other hand, contain in the situation of silicon compound of transition metal preferred transition metal silicon (compound that is only formed by transition metal and silicon), transition metal Si oxide, transition metal silicon nitride, transition metal silicon-oxygen nitride, transition metal silica carbonide, transition metal silicon carbonitride compound, transition metal silica carbonitride compound in use.Use the material that ratio is preferably following ranges that contains of each element: silicon is 10 atom %～80 atom %, is 30 atom %～50 atom % especially; Oxygen is 0 atom %～60 atom %, is less than or equal to 40 atom % especially greater than 0 atom %; Nitrogen is 0 atom %～57 atom %, is 20 atom %～50 atom % especially; Carbon is 0 atom %～20 atom %, is greater than 0 atom % and less than or equal to 5 atom % especially; Transition metal is 0 atom %～35 atom %, is 1 atom %～20 atom % especially, the film that can obtain having the object penetrating rate by suitable adjustment thickness.In addition, same with the situation of chromium compound, if in the too high situation of reflectivity, generally increase thickness by improving the containing ratio of light element, can form the film that has the object penetrating rate and have the reflectivity of requirement.
On the other hand, photomask is for by overlapping with semi-transparent film, when using as mask, and will be through the light intensity decays of semi-transparent film and photomask to making resist substantially go up film below photostable degree.Transmissivity is according to the exposure method of the situation of using mask and different, usually, under the combination of semi-transparent film, is preferably 0.001～10% transmissivity.
As the material of photomask, for example, can use transition metal, contain the silicon of transition metal, or in silicon, contain as required the material of the light elements such as aerobic, nitrogen, carbon, must be and semi-transparent film between alternative etched material.
Preferred material as photomask, can enumerate chromium, tantalum, molybdenum, tungsten particularly, the transistion metal compounds (particularly not siliceous transistion metal compound) such as chromium compound, tantalum compound, molybdenum compound, tungsten compound contain the silicon compound that is selected from the transition metal more than a kind in titanium, vanadium, cobalt, nickel, zirconium, niobium, molybdenum, hafnium, tantalum and the tungsten, silicon compound (silicon compound that does not particularly contain transition metal) etc.
Especially, in semi-transparent film, used in the situation of chromium or chromium compound, as the preferred material of photomask, can enumerate tantalum, molybdenum, tungsten, tantalum compound, molybdenum compound, tungsten compound and be selected from silicon compound, the silicon compound of the transition metal more than a kind in titanium, vanadium, cobalt, nickel, zirconium, niobium, molybdenum, hafnium, tantalum and the tungsten, especially can preferably use the silicon compound that contains molybdenum or the silicon compound of easy etching and processing.
These materials for the known wet etching of chromium and chromium compound or dry ecthing condition (for example, having used chlorine is the etching of gas) have an elching resistant, in addition, can not utilize known wet etching or dry ecthing condition (for example, having used fluorine is the etching of gas) to process under etching chromium and the chromium compound.
As photomask, use is selected from the silicon compound of the transition metal more than a kind in titanium, vanadium, cobalt, nickel, zirconium, niobium, molybdenum, hafnium, tantalum and the tungsten, or in the situation of silicon compound, from the material of following ranges: silicon is 10 atom %～95 atom %, is 30 atom %～95 atom % especially; Oxygen is 0 atom %～50 atom %, is greater than 0 atom % and less than or equal to 30 atom % especially; Nitrogen is 0 atom %～40 atom %, is 1 atom %～20 atom % especially; Carbon is 0 atom %～20 atom %, is greater than 0 atom % and less than or equal to 5 atom % especially; Transition metal is 0 atom %～35 atom %, is 1 atom %～20 atom % especially, after having considered the design thickness of photomask, can transmissivity as requested sets the ratio that contains of each element.
On the other hand, in semi-transparent film, used tantalum, molybdenum, tungsten, tantalum compound, molybdenum compound, tungsten compound, contained in the situation of the silicon compound that is selected from the transition metal more than a kind in titanium, vanadium, cobalt, nickel, zirconium, niobium, molybdenum, hafnium, tantalum and the tungsten or silicon compound, by in photomask, using chromium or chromium compound, preferably containing chromium and be selected from the chromium compound more than a kind (chromium compound that does not particularly contain silicon) in oxygen, nitrogen and the carbon, make the selective etch with semi-transparent film become possibility.
These materials are for tantalum, molybdenum, tungsten, tantalum compound, molybdenum compound, tungsten compound, contain and be selected from titanium, vanadium, cobalt, nickel, zirconium, niobium, molybdenum, hafnium, the silicon compound of the transition metal in tantalum and the tungsten more than a kind, and the known wet etching of silicon compound or dry ecthing condition are (for example, having used fluorine is the etching of gas) have an elching resistant, in addition, at etching tantalum not, molybdenum, tungsten, tantalum compound, molybdenum compound, tungsten compound, contain and be selected from titanium, vanadium, cobalt, nickel, zirconium, niobium, molybdenum, hafnium, the silicon compound of the transition metal in tantalum and the tungsten more than a kind, and under the silicon compound, can utilize known wet etching or dry ecthing condition (for example, having used chlorine is the etching of gas) to process.
Use as photomask in the situation of chromium compound, from the material of following ranges: chromium is more than or equal to 30 atom % and less than 100 atom %, is more than or equal to 60 atom % and less than 100 atom % especially; Oxygen is 0 atom %～60 atom %, is greater than 0 atom % and less than or equal to 50 atom % especially; Nitrogen is 0 atom %～50 atom %, is greater than 0 atom % and less than or equal to 40 atom % especially; Carbon is 0 atom %～30 atom %, is greater than 0 atom % and less than or equal to 20 atom % especially, after having considered the design thickness of photomask, can transmissivity as requested sets the ratio that contains of each element.
In the situation that all material, the part of photomask is become compare with other layer to make the anti-reflection layer that transmissivity improves and form.The exposure light wavelength that is considered as the situation of gray mask use decides the bed thickness of anti-reflection layer.In addition, for the adjustment of transmissivity and reflectivity, can adopt the method same with the situation of above-mentioned semi-transparent film.
The thickness of semi-transparent film can be made as 1nm～200nm, be preferably 5nm～100nm, the thickness of photomask is made as 5nm～500nm, be preferably 10nm～200nm.If thickness satisfies the optical characteristics of the regulations such as transmissivity, reflectivity, thin thickness processability is good, therefore preferred, but in order to accelerate etching speed, adding the light element such as N (nitrogen) after having satisfied the transmissivity of regulation, from the viewpoint of processability, preferably set composition and thickness that etching speed becomes the fastest.
Among the present invention, in addition, for the reflectivity of semi-transparent film (semi light transmitting part) and photomask (light shielding part), be formed on than the semi-transparent film under the provision wavelengths of the long wavelength side of light wavelength of exposing and the reflection differences of photomask, make it greater than the reflection differences under the exposure light wavelength.
At first, key property as mask, must prevent the generation of the ghost image pattern that the multipath reflection between mask and the substrate causes, as mentioned above, semi-transparent film (semi light transmitting part), photomask (light shielding part) are less than or equal to 30% under the exposure light wavelength, but only merely the reflectivity under the exposure light wavelength is designed to less than or equal to 30% with semi-transparent film and photomask, can not use reflectivity mutually to identify semi-transparent film and photomask.Usually, the provision wavelengths that is used for identification and reads the product information signs such as the product machining identification such as telltale mark and mask information mark is different from the exposure light wavelength, usually, uses the light of the wavelength of the wavelength side longer than the exposure light wavelength.In addition, the reflectivity of semi-transparent film and photomask is various because of wavelength.Therefore, among the present invention, use the large material of reflection differences under the reflection differences ratio exposure light wavelength of the semi light transmitting part under such provision wavelengths and light shielding part.
Thus, semi-transparent film and photomask are when making gray mask with the gray mask base, by from the either side of the pros and cons of the gray mask light to semi light transmitting part and light shielding part irradiation afore mentioned rules wavelength, utilize both reflection differences can identify semi light transmitting part and light shielding part.
In addition, by making semi-transparent film and the photomask reflection differences under the wavelength of the regulation longer than the exposure light wavelength become large, when having the product information sign such as the product machining identification such as telltale mark and mask information mark at semi-transparent film or photomask, can read these signs.Therefore, only the film etching and processing of folk prescription is made these signs for the sign shape that needs, just so that the identification of these signs, read and become possibility.
Semi-transparent film and photomask are more large more preferred in the reflection differences that reads under the wavelength of sign, correctly identify, read in order to utilize reading device, from the either side of the pros and cons of the gray mask light time to semi light transmitting part and light shielding part irradiation provision wavelengths, preferred light shielding part and the reflection differences of semi light transmitting part under provision wavelengths are more than or equal to 10%.In this case, in order to read sign from the film side, can satisfy above-mentioned relation from the reflectivity of film side, the reflectivity of substrate-side can satisfy above-mentioned relation when reading from substrate-side.
In addition, the wavelength of regulation is the inspection wavelength of gray mask base and gray mask, in the situation especially for the wavelength of the inspection of defective etc., adopt and use the same method, but the defect recognition position is semi-transparent film or photomask.
Reflectivity is subject to the strong effect of the light element contents such as oxygen, nitrogen, carbon especially because of the variation of wavelength.When light element content is high, has the tendency, particularly light element that reduce at the reflectivity of long wavelength side and tail off, when membrane material has metallicity strongly, uprising than the reflectivity under the wavelength of the long wavelength side of ripple that is used for exposure.
Therefore, in order to make between semi-transparent film and the photomask, reflection differences under the provision wavelengths of the wavelength side that this exposure light wavelength is grown is greater than the reflection differences under the exposure light wavelength, for example, can carry out following selection: make under the provision wavelengths of film at long wavelength side that reflectivity is high under the exposure light wavelength higher than another film reflectivity, perhaps, can carry out following selection: make under the provision wavelengths of film at long wavelength side that reflectivity is low under the exposure light wavelength lower than another film reflectivity.In addition, no matter semi-transparent film and photomask in the size of the reflectivity of exposure under the light wavelength, also can be considered the wavelength dependency of reflectivity, make in the reflection differences of second light-transmissive film of provision wavelengths of long wavelength side and photomask larger than the exposure light wavelength.
Especially, in order to make the reflection differences under the provision wavelengths of exposure light wavelength and the wavelength side longer than the exposure light wavelength large, towards the afore mentioned rules wavelength, a side increases the reflectivity of preferred semi-transparent film and photomask and the opposing party reduces by the exposure light wavelength.In addition, preferred semi-transparent film is opposite with the wavelength dependency of the reflectivity of photomask.So-called wavelength dependency is opposite, refer to shown in following condition (1) or (2), opposite in semi-transparent film and photomask in the magnitude relationship of the reflectivity under the exposure light wavelength and the reflectivity under the afore mentioned rules wavelength of the wavelength side longer than the exposure light wavelength.
(1) photomask is at the reflectivity of the reflectivity＜photomask under the exposure light wavelength under the provision wavelengths of the wavelength side longer than the exposure light wavelength
Semi-transparent film is at the reflectivity of the reflectivity under the exposure light wavelength＞semi-transparent film under the provision wavelengths of the wavelength side longer than the exposure light wavelength
(2) photomask is at the reflectivity of the reflectivity＞photomask under the exposure light wavelength under the provision wavelengths of the wavelength side longer than the exposure light wavelength
Semi-transparent film is at the reflectivity of the reflectivity under the exposure light wavelength＜semi-transparent film under the provision wavelengths of the wavelength side longer than the exposure light wavelength
In addition, also photomask and semi-transparent film can be made the multi-ply construction of formation with anti-reflection layer etc.Especially, by photomask being made the structure with light shield layer and anti-reflection layer, form the effect that anti-reflection layer is born be reduced in the reflectivity under the exposure light wavelength, make light shield layer bear the formation of interception, can take into account the reduction of filming and reflectivity.In this case, by regulating optical characteristics, the thickness of anti-reflection layer, also can satisfy the reflectivity of semi-transparent film and photomask.
For example, in the situation that light shield layer forms anti-reflection layer, the wavelength dependency of the reflectivity of semi-transparent film is in the situation that to compare under the afore mentioned rules wavelength reflectivity low with the exposure light wavelength, also can be by adjusting the anti-reflection layer on the light shield layer, reach minimum wavelength ratio exposure light wavelength is short and can realize thereby set reflectivity that thickness produces interference effect.Particularly, suppose the minimal value λ of the reflectivity when phase place in the bed interface does not have skew (minimum) Min, be made as n in the refractive index with antireflection film, when thickness is made as d, λ Min=1/ (4nd), λ MinLess than the exposure light wavelength, afore mentioned rules wavelength (λ Max) can be greater than λ Max=1/ (2nd).
There is no particular restriction to exposure light, preferably more than or equal to 350nm and have the light of peak wavelength between less than 500nm, the light of wavelength 436nm (g line), 405nm (h line) or 365nm (i line) particularly preferably perhaps comprises the light of at least a kind of wavelength of above-mentioned wavelength.In addition, exposure light can be the light (coherent lights of laser etc.) of single wavelength, can be the light (light with wave spectrum) with wavelength width, in the latter's the situation, preferably will be selected from least a kind of wavelength of 436nm, 405nm and 365nm as the light of peak wavelength, more preferably any wavelength is the light of peak-peak wavelength.In addition, the exposure light wavelength is the light wavelength of using when using gray mask to carry out pattern transfer, in the situation of the light of single wavelength only of exposing, be its wavelength, having in the situation of light of wavelength width is its peak wavelength, has in the situation of light of a plurality of peak wavelengths will demonstrate the peak wavelength of maximum intensity in them as the exposure light wavelength.
On the other hand, as the provision wavelengths of the wavelength side longer than the exposure light wavelength, for example, can use wavelength more than or equal to the light of 500nm.In addition, the upper limit of this provision wavelengths is generally less than or equal to 1000nm.As the wavelength of this regulation, the defect inspection that is suitable for gray mask base or gray mask is read with wavelength etc. with wavelength, product machining identification or product information sign.More specifically, the wavelength of using as defect inspection, can enumerate 488nm (argon laser), 532nm (the second higher hamonic wave of YAG), 633nm (He-Ne laser) etc., as the wavelength that reads usefulness of product machining identification or product information sign, can enumerate 546nm (e line) etc.
The film build method of semi-transparent film and photomask, applicable known method is not particularly limited, and when using sputtering method, because the restriction of membrane material is few, can obtain the film of homogeneous, so preferred.Can adjust the amount of sputtering target, sputter gas (atmosphere gas and reactant gas) and membrance casting condition etc., carry out the film forming of semi-transparent film and photomask with the film physical property (reflectivity, transmissivity etc.) that forms regulation.
Made the method for gray mask by the gray mask base, can be suitable for and be made by photo blanks the same method of known lithographic process of photomask.When this lithography, can form the product information signs such as the product machining identification such as telltale mark and mask information mark.
For example, by being on the transparency carrier that lamination successively has painting erosion resistant agent on the photomask of gray mask base of semi-transparent film and photomask, expose, development, etching, peel off resist, thereby can utilize photomask formation to be manufactured with product machining identification and the product information sign of literal, decorative pattern, bar code etc.During this photomask of etching, semi-transparent film stops thing to play a role as the etching of photomask.In addition, for simplifying working process, usually in the circuit pattern that forms photomask, form sign at photomask,
Secondly, by painting erosion resistant agent again, use the product machining identification (telltale mark) that forms to carry out position alignment, expose, development, etching, peel off resist, can form semi light transmitting part.At this moment, the part that has formed product machining identification and product information sign (is removed photomask, the part that expose on semi-transparent film surface) semi-transparent film can be removed also in the etching of semi-transparent film and can not remove, in the situation that used gray mask base of the present invention, even do not remove this part semi-transparent film, also can identify, read these product machining identifications and product information sign.
Like this, on transparency carrier, form successively semi-transparent film and photomask, form at the photomask of face side in the situation of product machining identification and product information sign, can after having formed semi-transparent film, photomask, form the pattern of sign at the photomask of face side.In addition, also can on transparency carrier, form successively photomask and semi-transparent film, in semi-transparent film formation product machining identification and the product information sign of face side, in this case, can after having formed photomask, semi-transparent film, form the pattern of sign at the semi-transparent film of face side.
When the film of face side forms sign, can form simultaneously the mask patterns such as circuit pattern, and, during with the film patterning of substrate-side, owing to can utilize this sign (telltale mark), therefore preferred.Especially, when the film of face side is photomask, owing to can utilize the having or not of film of face side that the reflectivity of transmissivity and substrate surface side is significantly changed, therefore particularly preferably.
In addition, the example that has formed sign at the film of face side has been shown in above-mentioned, but as gray mask, also can have formed sign at the film of substrate-side.When the film of substrate-side forms sign, can behind the film formation pattern of substrate-side, form the film of face side.For example, can by forming photomask at transparency carrier, semi-transparent film will be formed behind the photomask patterning, thereafter with semi-transparent film patterning, perhaps by forming semi-transparent film at transparency carrier, will form photomask behind the semi-transparent film patterning, thereafter the photomask patterning is made.
In addition, gray mask base of the present invention is according to the gray mask base that satisfies the regulation technical characterictic and form under the exposure light wavelength of semi-transparent film and photomask and afore mentioned rules wavelength, except lamination has the gray mask base of the semi-transparent film of patterning not and photomask, for example, also can be the gray mask base that will be behind the film patterning of substrate-side forms the film of the face side film patterning of face side (not with).
Gray mask base of the present invention and gray mask are suitable as FPD (flat-panel monitor).
[the second embodiment]
At first, the suitable object lesson as the second embodiment of the present invention is illustrated.
Gray mask base of the present invention has semi-transparent film and photomask at transparency carriers such as quartz base plates, for example, as shown in Figure 5, form them from transparency carrier 5 sides according to the antireflection film (the first antireflection film) 7 of the reflectivity of semi-transparent film 6, the semi-transparent film of adjustment, the order of photomask 8.Semi-transparent film 6, the first antireflection film 7 is the films that are used to form the semi light transmitting part of gray mask, photomask 8 is the films that are used to form the light shielding part of gray mask, after making gray mask with such gray mask base as starting material, semi-transparent film 6, adjust antireflection film (the first antireflection film) 7 and the photomask 8 of the reflectivity of semi-transparent film, as shown in Figure 6, become the semi light transmitting part of gray mask (in this case, comprise semi-transparent film and the first antireflection film, do not contain photomask) 61, light shielding part (in this case, comprise semi-transparent film, the first antireflection film and photomask) 81, the part of in addition, having removed both becomes transmittance section 51.
Gray mask of the present invention has transmittance section, semi light transmitting part and light shielding part.The transmittance section is generally the part that transparency carrier exposes, and has the transmissivity that exposure is contributed.In addition, light shielding part has the effect of exposure light being carried out shading on the degree that exposure is not contributed.On the other hand, semi light transmitting part has the transmissivity lower and higher than the transmissivity of light shielding part than the transmissivity of transmittance section, and has the transmissivity that contributes for exposure for exposure light.In addition, antireflection film (the first antireflection film) and photomask that the semi-transparent film that forms at the gray mask base, the reflectivity of double light-transmissive film are adjusted, photomask has the effect of exposure light being carried out shading with the degree that exposure is not contributed, semi-transparent film and the first antireflection film all have the transmissivity lower and higher than the transmissivity of photomask than the transmissivity of transparency carrier for exposure light with them, and have the transmissivity that exposure is contributed.
Gray mask base of the present invention possesses semi-transparent film at transparency carrier, adjusts antireflection film (the first antireflection film) and the photomask of the reflectivity of semi-transparent film, and these films form according to the order of semi-transparent film, the first antireflection film, photomask from above-mentioned transparent substrate side.By forming such formation, when only photomask having been carried out etching, by making antireflection film as the outmost surface layer of film, can reduce reflectivity.
For reducing the reflectivity of film self, thereby generally also can reduce to a certain degree reflectivity by adding oxygen, nitrogen etc., but not only the reduction effect of reflectivity is not enough, and because the shading characteristic of light reduces, has the problem be used to the thickness thickening that obtains the regulation transmissivity.In addition, large with the phase difference variable of transmittance section during the thickness thickening of semi-transparent film, form than the low part of semi-transparent part transmissivity on the border of transmittance section and semi light transmitting part, also have the problem of the design of forming part different with light-proofness.
In contrast to this, among the present invention, by forming antireflection film at semi-transparent film, make the thickness attenuation of the part of bearing semi-transparent effect, not only improve processability, and diminish by the phase differential that makes transmittance section and semi light transmitting part, can correctly form pattern.In addition, compare when not having antireflection film with each film of semi-transparent film, the phase place of the film by making a side is leading, and the opposing party's phase place is lagged behind, the phase differential of semi light transmitting part and transmittance section is diminished, also can further reduce the decline of transmissivity on the border of semi light transmitting part and transmittance section.
In addition, compare with photomask by semi-transparent film and to be positioned at substrate-side, with having formed the gray mask base patterning (operation of film forming needn't be set behind the patterning of film again) of whole films, can form gray mask.
The antireflection film (hereinafter referred to as the first antireflection film) of adjusting the reflectivity of semi-transparent film and photomask etching characteristic not simultaneously, can control only the photomask etching is removed well preferably former.When the etching characteristic of the first antireflection film and photomask is identical, be difficult to precision well only with the photomask etching, during the etching photomask, also with the first antireflection film etching, photomask is partly residual, may become produce semi light transmitting part transmissivity in face and the reason that fluctuates between substrate.In addition, make the first antireflection film and photomask etching characteristic not simultaneously, have advantages of that also the reflectivity that easily makes in the face distributes certain.
In addition, the etching characteristic of the first antireflection film and semi-transparent film can be identical, also can be different.When making the etching characteristic of the first antireflection film and semi-transparent film identical, etching the first antireflection film and semi-transparent film can be simplified mask manufacturing process simultaneously.
On the other hand, make the etching characteristic of the first antireflection film and semi-transparent film not simultaneously, the first antireflection film can play a role as the etching mask of semi-transparent film, can control and process well semi-transparent film.Do not using under the first antireflection film, also photomask can be played a role as etching mask, but when making photomask obtain regulation transmissivity (obscurity), owing to thickness need to be thickeied, even use also is difficult to fully improve machining precision as etching mask.By the first antireflection film is played a role as etching mask, can effectively improve the machining precision of semi-transparent film.
For the etching characteristic that makes the first antireflection film and photomask different, for example, can be with by CF 4, SF 6Be that etching gas carries out dry ecthing and is the film of etching gas with tolerance and be that the dry ecthing of etching gas has tolerance and is the combination that etching gas carries out etched film by above-mentioned chlorine oxygen to utilizing above-mentioned fluorine to the chlorine oxygen of the so chloride and oxygen of the mixed gas of chlorine and oxygen etc. fluorine-containing fluorine.
Particularly, for example, can be set as the first antireflection film is that etching gas carries out dry ecthing and is that etching gas has tolerance to chlorine oxygen by fluorine, and photomask is that the dry ecthing of etching gas has tolerance and is that etching gas carries out etching by chlorine oxygen to utilizing fluorine.
In the different situation of the etching characteristic of the first antireflection film and photomask, can make the photomask pattern become mask, with the first antireflection film patterning, but this moment, in the identical situation of the etching characteristic of the first antireflection film and semi-transparent film, for example, semi-transparent film is that etching gas carries out dry ecthing and is that etching gas has in the situation of tolerance for chlorine oxygen by fluorine, can utilize with resist during as mask etching the first antireflection film same fluorine be the semi-transparent film of etchant gas.In addition, because the consumption of resist is few, can utilize thin well etching of resist film precision.
On the other hand, in the different situation of the etching characteristic of the first antireflection film and semi-transparent film, for example, semi-transparent film is that the dry ecthing of etching gas has tolerance to utilizing fluorine, be that etching gas carries out in the etched situation by chlorine oxygen, the first antireflection film can be formed pattern as etching mask with semi-transparent film.When the etching characteristic of photomask and semi-transparent film is identical, owing to can remove simultaneously at the residual photomask of the part that will become semi light transmitting part with the etching of semi-transparent film, therefore has advantages of and to simplify gray mask manufacturing process.In addition, can utilize chlorine oxygen is that double light-transmissive film of etching gas carries out etched situation to have advantages of that substrate is not easy roughened.
In addition, also can to make photomask be the etching gas dry ecthing by fluorine and be that etching gas has tolerance to chlorine oxygen, and the first antireflection film is that the dry ecthing of etching gas has tolerance and is etchant gas by chlorine oxygen to utilizing fluorine.
Form in the situation of such formation, carry out etching with resist as mask during with the photomask patterning, can reduce the film consumption of resist, can utilize thin resist film to form pattern, but precision form the also little good photomask pattern of thick close dependence well.In the different situation of the etching characteristic of the first antireflection film and photomask, can be with the first antireflection film patterning as mask with the photomask pattern, in the identical situation of the etching characteristic of the first antireflection film and semi-transparent film, for example, semi-transparent film is that the dry ecthing of etching gas has tolerance and is under the situation of etchant gas by chlorine oxygen to utilizing fluorine, can form pattern with the first antireflection film while semi-transparent film of etching, afterwards, can by only removing the photomask as the mask of the part that will become semi light transmitting part, form pattern.Especially, when being the etchant gas photomask with chlorine oxygen, substrate is not easy etching, can prevent the coarse and gonorrhoea of substrate surface.
On the other hand, in the different situation of the etching characteristic of the first antireflection film and semi-transparent film, for example, semi-transparent film is that etching gas carries out dry ecthing and is that etching gas has in the situation of tolerance to chlorine oxygen by fluorine, the first antireflection film can be formed pattern as etching mask with semi-transparent film.When the etching characteristic of photomask and semi-transparent film is identical, owing to can remove simultaneously at the residual photomask of the part that will become semi light transmitting part with the etching of semi-transparent film, therefore has advantages of and to simplify gray mask manufacturing process.
As the concrete material of film, as being the etching gas dry ecthing with fluorine, be that etching gas can't etched material with chlorine oxygen, by using silicon, silicon compound, can satisfy such etching characteristic.As silicon compound, preferably comprise at least silicon and transition metal, for example, making transition metal and silicon is MoSi, TaSi, ZrSi, WSi etc., also preferably contains the light elements such as aerobic, nitrogen, carbon.Can be by changing thickness, composition, for example the amount of light element, particularly oxygen and nitrogen is adjusted the transmissivity (light-proofness) of film.
As such material, particularly, such as enumerating MoSiN, MoSiON, MoSiO, TaSiON, TaSiN, TaSiO, ZrSiON, ZrSiN, ZrSiO, WSiON, WSiN, WSiO etc.Wherein, the especially easily etching of dry ecthing that MoSiON, MoSiN with fluorine are, tolerance is good in the dry ecthing of chlorine oxygen system, therefore preferred.The ratio of components of the Constitution Elements of film, for example, can for: transition metal is 0 atom %～70 atom %, be greater than 0 atom % and less than or equal to 30 atom % especially, silicon is 20 atom %～100 atom %, is more than or equal to 40% and less than 100 atom % especially, oxygen is 0 atom %～70 atom %, be greater than 0 atom % and less than or equal to 60 atom % especially, nitrogen is 0 atom %～60 atom %, is greater than 0 atom % and less than or equal to 50 atom % especially.
In addition, as being the material of etchant gas and the etchant gas that is not by fluorine with chlorine oxygen, contain chromium thing (chromium or chromium compound) by use and can satisfy characteristic.As chromium compound, preferably contain compound, the especially not siliceous compound of the light elements such as chromium and oxygen, nitrogen, carbon.Can be by changing thickness, composition, for example the amount of light element, particularly oxygen and nitrogen is adjusted the transmissivity (light-proofness) of film.
As such material, can enumerate particularly such as CrC, CrCN, CrCO, CrCON, CrN, CrON, CrO etc.The proportion of composing of the Constitution Elements of film as can for: chromium is greater than 0 atom % and less than or equal to 100%, 20 atom %～100 atom % particularly, carbon is 0 atom %～30 atom %, be greater than 0 atom % and less than or equal to 20 atom % especially, oxygen is 0 atom %～60 atom %, be greater than 0 atom % and less than or equal to 50 atom % especially, nitrogen is 0 atom %～50 atom %, is greater than 0 atom % and less than or equal to 40 atom % especially.
Formation as film, more specifically, can be with as the MoSiN of semi-transparent film, as the MoSiN of the first antireflection film, as the CrN combination of photomask, and will be as the CrN of semi-transparent film, as the MoSiN of the first antireflection film, as the combinations such as CrN of photomask, but be not limited to them.
Either one or both can also can be multilayer for individual layer in semi-transparent film, the photomask, in addition, can form composition in the different formation of film thickness direction, also can adjust the characteristic that makes optical characteristics satisfy regulation.
The film build method of these semi-transparent films and photomask is not particularly limited, and when using sputtering method, the restriction of membrane material is few, can obtain the film of homogeneous.In sputtering method, use contains the target of the transition metal (such as Mo, Ta, Zr, W) that consists of film and/or silicon or chromium target etc., for the optical characteristics that obtains stipulating, can be according to the light element that consists of film, adjust the amount of oxygen-containing gas, nitrogenous gas, carbonaceous gas isoreactivity gas and membrance casting condition (for example, the formation of target, electric weight that target is applied etc.) etc.
The transmissivity of semi light transmitting part is between light shielding part and transmittance section, namely, transmissivity than the transmittance section is low and higher than the transmissivity of light shielding part, using method according to the mask that obtains is adjusted it, usually, semi-transparent film and the first antireflection film are combined, for example are 10～80%, more generally are 15～60%.
In addition, because the transmissivity of light shielding part is the transmissivity of exposure light being carried out shading with the degree that exposure is not contributed, thus semi-transparent film, the first antireflection film and photomask are combined, for example, can be for more than or equal to 2 on optical concentration, be preferably more than and equal 3.
In addition, by carrying out the transmissivity adjustment take semi-transparent film as main, utilize the first antireflection film to carry out the reduction of reflectivity, the design of film becomes easily, and the reduction effect of thickness is also large, and therefore the optical concentration of the first antireflection film is preferably little than semi-transparent film.
As the thickness of each film, can adjust to satisfy above-mentioned optical characteristics, for example, can make semi-transparent film is 3～100nm, is 3～80nm especially, and the first antireflection film is 5～30nm, is 5～20nm especially, and photomask is 40～200nm.
Exposure light is not particularly limited, preferably more than or equal to 350nm and have the light of peak wavelength between less than 500nm, especially, preferably have and be selected among 436nm (g line), 405nm (h line) and the 365nm (i line) at least a kind of wavelength as the light of peak wavelength.In addition, exposure light can be the light (coherent lights of laser etc.) of single wavelength, also can be the light (light with wave spectrum) with wavelength width.
For substrate, as long as to above-mentioned exposure optical transparency, can be synthetic quartz, soda-lime glass etc., synthetic quartz is preferred because thermal expansion is little.
In addition, when on photomask, further forming the second antireflection film, owing to can reduce the reflectivity of photomask therefore preferred.Arrange in the situation of the second antireflection film, the etching characteristic of preferred the second antireflection film and photomask is identical.Particularly, preferred photomask and the second antireflection film carry out dry ecthing and chloride and etching gas oxygen are had tolerance by fluorine containing etchant gas, and perhaps photomask and the second antireflection film all have tolerance and carry out etching by chloride and etching gas oxygen the dry ecthing that utilizes fluorine containing etchant gas.
The antireflection film, adaptation that in addition, can further form other between semi-transparent film and substrate improve film, be used for improving the basalis of surfaceness etc.
Can make gray mask by the gray mask base with known lithographic method.Particularly, can enumerate following method.
(manufacture method 1) semi-transparent film situation identical with the etching characteristic of the first antireflection film
For example, use forms according to the order of semi-transparent film, the first antireflection film, photomask, the second antireflection film on quartz base plate, making semi-transparent film and the first antireflection film is the identical film of etching characteristic, photomask and the second antireflection film are the film of same etch characteristic, and the first antireflection film is the gray mask base that the different film of etching characteristic forms with photomask.
Substrate and the film that forms directly over it for example etching characteristic of semi-transparent film can be the same or different, and not simultaneously, owing to substrate is not carried out over etching, the phase differential that sees through the light of semi light transmitting part and transmittance section can not become greatly, therefore preferably.
At first, painting erosion resistant agent on the second antireflection film.Resist can also can be eurymeric for minus.Use in the situation of eurymeric resist, carry out and to become the describing (exposure), develop formation resist pattern of part of transmittance section.Secondly, the resist pattern as mask, had elching resistant at the first antireflection film, dry ecthing under the etching condition of etching photomask and the second antireflection film.Etching also can be wet etching.At this moment, because the first antireflection film stops thing to play a role as etching, etching is carried out in control well.Secondly, as mask, use the second antireflection film and photomask to have elching resistant, the etchant of etching the first antireflection film and semi-transparent film in the pattern of resist pattern and antireflection film, photomask, etching the first antireflection film and semi-transparent film form the transmittance section.Herein, although with the pattern of resist pattern and the second antireflection film, photomask as etching mask, resist can be removed, clean, the pattern of the second antireflection film, photomask is carried out etching as etching mask.
In the above-mentioned etching, set in the situation of resist thickness for resist is eliminated, after etching, to there is no need to remove resist and preferably.After the above-mentioned etching in the residual situation that resist arranged, after removing resist, cleaning, painting erosion resistant agent again.Resist can be that eurymeric also can be minus, in the situation of eurymeric, the describing of part (exposure) of carrying out becoming semi light transmitting part, develops, and forms the resist pattern.Secondly, as mask, have elching resistant by the first antireflection film with the resist pattern, the dried or wet etching of etching photomask and the second antireflection film, etching the second antireflection film and photomask, formation will become the part of semi light transmitting part., remove resist, finish gray mask thereafter.
More specifically, for example, can adopt following method.
On quartz base plate, form successively semi-transparent film, the first antireflection film, photomask and the second antireflection film, at semi-transparent film and the first antireflection film for by the dry ecthing of fluorine containing etchant gas and film that chloride and etching gas oxygen are had tolerance, photomask and the second antireflection film are for having the dry ecthing that utilizes fluorine containing etchant gas in tolerance and the situation by the film of the etchant gas of chloride and oxygen, at first, at the second antireflection film coating eurymeric resist, carry out to become the describing (exposure), develop of part of transmittance section, form the resist pattern.Secondly, the resist pattern as mask, is used mixed gas etching the second antireflection film and the photomask of chlorine and oxygen.At this moment, the first antireflection film stops thing to play a role as etching.Secondly, as mask, using as fluorine is the SF of gas with the pattern of resist pattern and the second antireflection film, photomask 6, etching the first antireflection film and semi-transparent film form the transmittance section.Secondly, after removing resist, cleaning, painting erosion resistant agent again carries out and will become the describing (exposure), develop formation resist pattern of part of semi light transmitting part.Secondly, as mask, with mixed gas etching the second antireflection film and the photomask of chlorine and oxygen, formation will become the part of semi light transmitting part with the resist pattern., remove resist, finish gray mask thereafter.
Different with the etching characteristic of the first antireflection film and identical with the photomask situation of (manufacture method 2) semi-transparent film
For example, use forms according to the order of semi-transparent film, the first antireflection film, photomask, the second antireflection film on quartz base plate, making semi-transparent film, photomask and the second antireflection film is the identical film of etching characteristic, the gray mask base that the first antireflection film forms for the film different from semi-transparent film, photomask and the second antireflection film etching characteristic.
Substrate and the film that directly over it, forms, for example the etching characteristic of semi-transparent film can be the same or different, and not simultaneously, owing to substrate is not carried out over etching, the phase differential that sees through the light of semi light transmitting part and transmittance section can not become greatly, therefore preferred.
At first, painting erosion resistant agent on the second antireflection film.Resist can also can be eurymeric for minus.Use in the situation of eurymeric resist, carry out and will become the describing (exposure), develop of part of transmittance section, thus formation resist pattern.Secondly, the resist pattern as mask, had elching resistant at the first antireflection film, dry ecthing under the etching condition of etching photomask and the second antireflection film.Etching also can be wet etching.At this moment, because the first antireflection film stops thing to play a role as etching, etching is carried out in control well.Secondly, as mask, use the second antireflection film and photomask to have elching resistant in the pattern of resist pattern and the second antireflection film, photomask, the etchant of etching the first antireflection film, etching the first antireflection film, formation will become the part of transmittance section.Herein, although with the pattern of resist pattern and the second antireflection film, photomask as etching mask, resist can be removed, clean, the pattern of the second antireflection film, photomask is carried out etching as etching mask.
In the above-mentioned etching, set in the situation of resist thickness for resist is eliminated, after etching, to have there is no need to remove resist and preferred.After the above-mentioned etching in the residual situation that resist arranged after removing resist, cleaning, painting erosion resistant agent again.Resist can be that eurymeric also can be minus, in the situation of eurymeric, carry out with become the part of semi light transmitting part and will become the transmittance section the describing of part (exposure), develop, form the resist pattern.Secondly, has elching resistant by the first antireflection film, doing or wet etching of etching photomask and the second antireflection film and semi-transparent film, with the resist pattern as etching mask etching the second antireflection film and photomask, simultaneously with the pattern of the first antireflection film as the semi-transparent film of etching mask etching, thereby form the part that will become semi light transmitting part., remove resist, finish gray mask thereafter.
More specifically, for example, adopt following method.
On quartz base plate, form successively semi-transparent film, the first antireflection film, photomask and the second antireflection film, at the first antireflection film for by the dry ecthing of fluorine containing etchant gas and the film to utilizing chloride and etching gas oxygen to have tolerance, semi-transparent film, photomask and the second antireflection film are for having the dry ecthing that utilizes fluorine containing etchant gas in tolerance and the situation by the film of the etchant gas of chloride and oxygen, at first, at the second antireflection film coating eurymeric resist, carry out to become the describing of part (exposure) of transmittance section, develop, form the resist pattern.Secondly, the resist pattern as mask, is used mixed gas etching the second antireflection film and the photomask of chlorine and oxygen.At this moment, the first antireflection film stops thing to play a role as etching.Secondly, as mask, using as fluorine is the SF of gas with the pattern of resist pattern and the second antireflection film, photomask 6, etching the first antireflection film, formation will become the part of transmittance section.Secondly, after removing resist, cleaning, painting erosion resistant agent again carries out and will become the part of semi light transmitting part and will become the describing (exposure), develop formation resist pattern of part of transmittance section.Secondly, the resist pattern as mask, with mixed gas etching the second antireflection film and the photomask of chlorine and oxygen, when formation will become the part of semi light transmitting part, is come the semi-transparent film of etching with the pattern of the first antireflection film as etching mask., remove resist, finish gray mask thereafter.
In addition, in the example of the manufacture method of above-mentioned gray mask, show the situation with second antireflection film, but made by the gray mask base that does not form the second antireflection film under the situation of gray mask, can make the etching of the second antireflection film and photomask become the etching of photomask, the pattern that replaces utilizing the second antireflection film and photomask utilizes the pattern of photomask as etching mask as etching mask.
Embodiment
Embodiment and comparative example below are shown, the present invention is specifically described, but the present invention is not limited to following embodiment.
[embodiment 1]
By utilizing sputtering method at quartz base plate, in vacuum chamber, pass into Ar (5sccm), N 2(50sccm), O 2Gas (2sccm), air pressure is made as 9.0 * 10 -2Pa applies 750W, the Si target is applied 250W the MoSi target, as the semi-transparent film of MoSi, forms the MoSiON film of thickness 18nm.With the results are shown among Fig. 3 (C) of the transmissivity after the semi-transparent film film forming of mensuration.In this stage, the transmissivity under the wavelength (365nm) that uses as exposure light is 52.9%.
Secondly, form the Cr photomask of the sandwich construction that is formed by basalis, light shield layer and anti-reflection layer at this semi-transparent film.By utilizing sputtering method, in vacuum chamber, pass into Ar (10～50sccm), N 2(1～11sccm), N 2(0～12sccm) gas, air pressure is made as 0.1～0.2Pa to O, and the Cr target is applied 450～550W, thereby as the Cr photomask, forms the CrON film of thickness 71nm, obtains the gray mask base.By changing N 2, N 2The gas flow ratio of O, 2 layers of structure of the light shield layer of Cr photomask formation substrate-side and the anti-reflection layer of face side.With the results are shown among Fig. 3 (C) of the transmissivity after the mensuration photomask film forming.In this stage, the transmissivity under the wavelength (365nm) that uses as exposure light is 0.630%.
In addition, under these conditions, form separately respectively Cr photomask and the semi-transparent film of MoSi at quartz base plate, with the results are shown among Fig. 3 (A) and Fig. 3 (B) of mensuration reflectivity separately.In addition, Fig. 3 (A) is from film side, the result of Fig. 3 (B) for measuring from substrate-side.In this case, during with the reading wavelength and be made as 546nm of product machining identification and product information sign, for example, from the reflectivity of film side irradiation light time be: photomask is 36.7%, semi-transparent film is 17.4%, their difference enough greatly 19.3% when utilizing these photomasks and semi-transparent film to form product machining identification and product information sign, can be utilized reflected light identification, read product machining identification and product information sign.
In addition, use resist to semi-transparent film and the photomask of the gray mask base that obtains, be the dry ecthing of gas by the Cr photomask having been used chlorine, it is the dry ecthing of gas that the semi-transparent film of MoSi has been used fluorine, with each film patterning, the gray mask of transmittance section, semi light transmitting part and light shielding part that can form as shown in Figure 2 formation.
[embodiment 2]
By utilizing sputtering method at quartz base plate, in vacuum chamber, pass into Ar (10sccm), N 2The gas of O (12sccm), air pressure is made as 0.15Pa, and the Cr target is applied 590W, thereby has formed the CrON film of thickness 11nm as the semi-transparent film of Cr.With the results are shown among Fig. 4 (C) of the transmissivity after the semi-transparent film film forming of mensuration.In this stage, the transmissivity under the wavelength (365nm) that uses as exposure light is 58.2%.
Secondly, by utilizing sputtering method at this semi-transparent film, in vacuum chamber, pass into Ar (20～5sccm), N 2(10～5sccm) gas, air pressure is made as 6.0 * 10 -2Pa applies 230W to the MoSi target, and the Si target is applied 770W, thereby has formed the MoSiN film of thickness 60nm as the MoSi photomask, obtains the gray mask base.With the results are shown among Fig. 4 (C) of the transmissivity after the mensuration photomask film forming.In this stage, the transmissivity under the wavelength (365nm) that uses as exposure light is 5.36%.
In addition, under these conditions, form separately respectively MoSi photomask and the semi-transparent film of Cr at quartz base plate, with the results are shown among Fig. 4 (A) and Fig. 4 (B) of each reflectivity of mensuration.In addition, Fig. 4 (A) is from film side, the result of Fig. 4 (B) for measuring from substrate-side.In this case, during with the reading wavelength and be made as 546nm of product machining identification and product information sign, for example, from the reflectivity of film side irradiation light time be: photomask is 36.1%, semi-transparent film is 13.1%, their difference enough greatly 23.0% if utilize these photomasks and semi-transparent film to form product machining identification and product information sign, can be utilized reflected light identification, read product machining identification and product information sign.
In addition, semi-transparent film and photomask to the gray mask base that obtains use resist, be the dry ecthing of gas by the MoSi photomask having been used fluorine, it is the dry ecthing of gas that the semi-transparent film of Cr has been used chlorine, with each film patterning, the gray mask of transmittance section, semi light transmitting part and light shielding part that can form as shown in Figure 2 formation.
In above-described embodiment 1,2 in the situation of any, in the patterning of photomask, but the established part of etching photomask forms the product information signs such as the product machining identification such as telltale mark and mask information mark.In addition, when the semi-transparent film of etching, can utilize the product machining identifications such as telltale mark of formation to carry out position alignment, correctly with semi-transparent film patterning.
[embodiment 3]
Utilize sputtering method at quartz base plate, in vacuum chamber, pass into Ar (20sccm), N 2(5sccm), use MoSi target and Si target, form the MoSiN film of thickness 15nm as semi-transparent film.
Secondly, utilize sputtering method at this semi-transparent film, in vacuum chamber, pass into Ar (5sccm), N 2(50sccm), O 2(2sccm), use MoSi target and Si target, form the MoSiON film of thickness 31nm as the first antireflection film.Being 20% in the transmissivity in the stage that has formed the first antireflection film during at wavelength 365nm, is 15% from the reflectivity of the first antireflection film side under wavelength 365nm.
Secondly, utilize sputtering method at this first antireflection film, in vacuum chamber, pass into Ar (20sccm), N 2(1sccm), use the Cr target, form the CrN film of thickness 60nm as photomask.
In addition, at this photomask sputtering method, in vacuum chamber, pass into Ar (15sccm), N 2O (12sccm) uses the Cr target, forms the CrON film of thickness 20nm as the second antireflection film, obtains the gray mask base.
[comparative example 1]
Utilize sputtering method at quartz base plate, in vacuum chamber, pass into Ar (5sccm), N 2(50sccm), O 2(2sccm), use MoSi target and Si target, form the MoSiN film of thickness 80nm as semi-transparent film.Transmissivity in the stage that has formed semi-transparent film is 20% under wavelength 365nm, is 15% from the reflectivity of semi-transparent film side under wavelength 365nm.
Secondly, utilize sputtering method at this semi-transparent film, in vacuum chamber, pass into Ar (20sccm), N 2(1sccm), use the Cr target, form the CrN film of thickness 60nm as photomask.
In addition, utilize sputtering method at this photomask, in vacuum chamber, pass into Ar (15sccm), N 2O (12sccm) uses the Cr target, as antireflection film, forms the CrON film of thickness 20nm, obtains the gray mask base.
The gray mask base that obtains in the above-mentioned example by with each film of photoetching process (photolithography) etching, can form the gray mask with transmittance section, semi light transmitting part and light shielding part.Semi light transmitting part with respect to the gray mask that obtains in embodiment 3 is thickness 46nm (semi-transparent film 15nm and the first antireflection film 31nm), transmissivity 20%, reflectivity 15%, the semi light transmitting part of the gray mask that obtains in the comparative example 1 that obtains identical transmissivity and reflectivity is thickness 80nm (semi-transparent film is only arranged, and is 80nm).Therefore, by the present invention with the semi light transmitting part filming.
[embodiment 4]
Utilize sputtering method on the quartz base plate, in vacuum chamber, pass into Ar (20sccm), N 2(1sccm), use the Cr target, form the CrN film of thickness 12nm as semi-transparent film.
Secondly, utilize sputtering method at this semi-transparent film, in vacuum chamber, pass into Ar (5sccm), N 2(50sccm), use MoSi target and Si target, form the MoSiN film of thickness 12nm as the first antireflection film.Transmissivity in the stage that has formed the first antireflection film is 20% under wavelength 365nm, is 26% from the reflectivity of the first antireflection film side under wavelength 365nm.
Secondly, utilize sputtering method at this first antireflection film, in vacuum chamber, pass into Ar (20sccm), N 2(1sccm), use the Cr target, as photomask, form the CrN film of thickness 60nm.
In addition, utilize sputtering method at this photomask, in vacuum chamber, pass into Ar (15sccm), N 2O (12sccm) uses the Cr target, as the second antireflection film, forms the CrON film of thickness 20nm, obtains the gray mask base.
[embodiment 5]
Utilize sputtering method at quartz base plate, in vacuum chamber, pass into Ar (20sccm), N 2(1sccm), use the Cr target, form the CrN film of thickness 10nm as semi-transparent film.
Secondly, utilize sputtering method at this semi-transparent film, in vacuum chamber, pass into Ar (15sccm), N 2O (12sccm) uses the Cr target, forms the CrON film of thickness 11nm as the first antireflection film.Transmissivity in the stage that has formed the first antireflection film is 20% under wavelength 365nm, is 26% from the reflectivity of the first antireflection film side under wavelength 365nm.
In addition, utilize sputtering method at this first antireflection film, in vacuum chamber, pass into Ar (20sccm), N 2(5sccm), use MoSi target and Si target, as the MoSi photomask, form the MoSiN film of thickness 60nm, obtain the gray mask base.
[comparative example 2]
Utilize sputtering method at quartz base plate, in vacuum chamber, pass into Ar (15sccm), N 2O (12sccm) uses the Cr target, forms the CrN film of thickness 46nm as semi-transparent film.Transmissivity in the stage that has formed semi-transparent film is 20% under wavelength 365nm, is 28% from the reflectivity of semi-transparent film side under wavelength 365nm.
Secondly, utilize sputtering method at this semi-transparent film, in vacuum chamber, pass into Ar (20sccm), N 2(5sccm), use MoSi target and Si target, as the MoSi photomask, form the MoSiN film of thickness 60nm, obtain the gray mask base.
The gray mask base that obtains in the above-mentioned example by with photolithographic each film of method etching, can form the gray mask with transmittance section, semi light transmitting part and light shielding part.The semi light transmitting part of the gray mask that obtains in embodiment 4 is thickness 24nm (semi-transparent film 12nm and the first antireflection film 12nm), transmissivity 20%, reflectivity 26%, the semi light transmitting part of the gray mask that obtains among the embodiment 5 is thickness 21nm (semi-transparent film 10nm and the first antireflection film 11nm), transmissivity 20%, reflectivity 26%, and the semi light transmitting part of the gray mask that obtains in the comparative example 2, be 20% when thickness is combined for making transmissivity, thickness is that 46nm (only has semi-transparent film, 46nm), reflectivity is 28%.Semi light transmitting part of the present invention is had advantage by filming under any situation as can be known.

Claims (11)

1. gray mask base, it is the raw-material gray mask base that becomes gray mask, this gray mask has transmittance section, light shielding part and semi light transmitting part, above-mentioned light shielding part carries out shading with the degree that exposure is not contributed to exposure light, above-mentioned semi light transmitting part is for exposure light, have the transmissivity lower and higher than the transmissivity of above-mentioned light shielding part than the transmissivity of above-mentioned transmittance section, and have the transmissivity that exposure is contributed, it is characterized in that:
Be formed for forming the semi-transparent film and the photomask that is used to form above-mentioned light shielding part of above-mentioned semi light transmitting part at transparency carrier;
Above-mentioned semi-transparent film and photomask are formed by the film with mutually different etching characteristic;
Above-mentioned semi-transparent film and the photomask reflectivity under the exposure light wavelength is all less than or equal to 30%;
Be formed on than the above-mentioned semi-transparent film under the provision wavelengths of the long wavelength side of light wavelength of exposing and the reflection differences of photomask, make it greater than the reflection differences under the exposure light wavelength; And
Form above-mentioned semi-transparent film and photomask, so that when the gray mask base made gray mask, by from the either side of the pros and cons of the gray mask light to above-mentioned semi light transmitting part and light shielding part irradiation afore mentioned rules wavelength, can identify above-mentioned semi light transmitting part and light shielding part according to both reflection differences.
2. gray mask base claimed in claim 1 is characterized in that: in the reflectivity of above-mentioned semi-transparent film and photomask, from above-mentioned exposure light wavelength to above-mentioned provision wavelengths, a side increases, and the opposing party reduces.
3. gray mask base claimed in claim 1, it is characterized in that: above-mentioned exposure light is the light of wavelength 436nm, 405nm or 365nm, perhaps contains the light of at least a kind of wavelength in the above-mentioned wavelength.
4. gray mask base claimed in claim 1 is characterized in that: the wavelength of afore mentioned rules is for more than or equal to 500nm and less than or equal to the wavelength of 1000nm.
5. gray mask base claimed in claim 1 is characterized in that: the wavelength of afore mentioned rules be defect inspection with or product machining identification read with or the product information sign read the wavelength of usefulness.
6. gray mask base claimed in claim 1, it is characterized in that: from the either side of the pros and cons of the gray mask light time to above-mentioned semi light transmitting part and light shielding part irradiation afore mentioned rules wavelength, above-mentioned light shielding part and the reflection differences of above-mentioned semi light transmitting part under the afore mentioned rules wavelength are more than or equal to 10%.
7. gray mask base claimed in claim 1, it is characterized in that: above-mentioned photomask contains transition metal and silicon, and above-mentioned semi-transparent film contains chromium.
8. gray mask base claimed in claim 1, it is characterized in that: above-mentioned photomask contains chromium, and above-mentioned semi-transparent film contains transition metal and silicon.
9. gray mask base claimed in claim 1, it is characterized in that: above-mentioned gray mask base is flat-panel monitor gray mask base.
10. gray mask, this gray mask has transmittance section, light shielding part and semi light transmitting part, above-mentioned light shielding part carries out shading with the degree that exposure is not contributed to exposure light, above-mentioned semi light transmitting part has the transmissivity lower and higher than the transmissivity of above-mentioned light shielding part than the transmissivity of above-mentioned transmittance section for exposure light, and have the transmissivity that exposure is contributed, it is characterized in that:
Above-mentioned semi light transmitting part and light shielding part are formed by the film with mutually different etching characteristic;
Above-mentioned semi light transmitting part and the light shielding part reflectivity under the exposure light wavelength is all less than or equal to 30%;
Form above-mentioned semi light transmitting part and the light shielding part reflection differences under the provision wavelengths of the wavelength side longer than the exposure light wavelength, make it greater than the reflection differences under the exposure light wavelength; And
Form above-mentioned semi light transmitting part and light shielding part, so that by from the either side of the pros and cons of the gray mask light to above-mentioned semi light transmitting part and light shielding part irradiation afore mentioned rules wavelength, can identify above-mentioned semi light transmitting part and light shielding part according to both reflection differences;
Have the product machining identification or the product information sign that are formed by the above-mentioned light shielding part take above-mentioned semi light transmitting part as background or the above-mentioned semi light transmitting part take above-mentioned light shielding part as background.
11. the formation method of product machining identification or product information sign, it is to have the transmittance section, the gray mask of light shielding part and semi light transmitting part forms the method that the product machining identification that formed by above-mentioned semi light transmitting part and light shielding part or product information identify, above-mentioned light shielding part carries out shading with the degree that exposure is not contributed to exposure light, above-mentioned semi light transmitting part is for exposure light, have the transmissivity lower and higher than the transmissivity of above-mentioned light shielding part than the transmissivity of above-mentioned transmittance section, and has the transmissivity that exposure is contributed, it is characterized in that, use following gray mask base:
Be formed for forming the semi-transparent film and the photomask that is used to form above-mentioned light shielding part of above-mentioned semi light transmitting part at transparency carrier,
Form above-mentioned semi-transparent film and photomask as the film with mutually different etching characteristic,
Make above-mentioned semi-transparent film and the photomask reflectivity under the exposure light wavelength all less than or equal to 30%,
Be formed on than the above-mentioned semi-transparent film under the provision wavelengths of the long wavelength side of light wavelength of exposing and the reflection differences of photomask, make it greater than the reflection differences under the exposure light wavelength, and
Above-mentioned semi-transparent film and photomask have been formed so that when the gray mask base made gray mask, by from the either side of the pros and cons of the gray mask light to above-mentioned semi light transmitting part and light shielding part irradiation afore mentioned rules wavelength, can identify above-mentioned semi light transmitting part and light shielding part according to both reflection differences;
By the above-mentioned semi-transparent film of etching and photomask, utilize above-mentioned light shielding part or the above-mentioned semi light transmitting part take above-mentioned light shielding part as background, formation product machining identification or product information sign take above-mentioned semi light transmitting part as background.
CN 200910160207 2008-08-15 2009-07-30 Gray tone mask blank, gray tone mask and forming method of product machining identification or product information identification Active CN101650527B (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2008209128A JP4831368B2 (en) 2008-08-15 2008-08-15 Gray tone mask blank and gray tone mask
JP2008209125 2008-08-15
JP2008209125A JP4849276B2 (en) 2008-08-15 2008-08-15 Gray tone mask blank, gray tone mask, and method for forming product processing mark or product information mark
JP2008-209128 2008-08-15
JP2008209128 2008-08-15
JP2008-209125 2008-08-15

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN201210412083.6A Division CN102929096B (en) 2008-08-15 2009-07-30 Y-tone mask substrate and gray-tone mask

Publications (2)

Publication Number Publication Date
CN101650527A CN101650527A (en) 2010-02-17
CN101650527B true CN101650527B (en) 2013-03-27

Family

ID=41672787

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200910160207 Active CN101650527B (en) 2008-08-15 2009-07-30 Gray tone mask blank, gray tone mask and forming method of product machining identification or product information identification

Country Status (2)

Country Link
JP (1) JP4849276B2 (en)
CN (1) CN101650527B (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011215197A (en) * 2010-03-31 2011-10-27 Hoya Corp Photomask and method for manufacturing the same
JP5635577B2 (en) * 2012-09-26 2014-12-03 Hoya株式会社 Photomask manufacturing method, photomask, pattern transfer method, and flat panel display manufacturing method
JP6453780B2 (en) * 2013-03-12 2019-01-16 マイクロニック アーベーＭｙｃｒｏｎｉｃ Ａｂ Method and apparatus for mechanically formed alignment reference body
JP2014206471A (en) * 2013-04-12 2014-10-30 Ｓｃｉｖａｘ株式会社 Detection method for optical sensor
JP6266322B2 (en) * 2013-11-22 2018-01-24 Hoya株式会社 Phase shift mask blank for manufacturing display device, phase shift mask for manufacturing display device, method for manufacturing the same, and method for manufacturing display device
CN105451431B (en) * 2014-09-02 2018-10-30 鹏鼎控股(深圳)股份有限公司 Circuit board and preparation method thereof
CN114675486A (en) * 2016-08-26 2022-06-28 Hoya株式会社 Mask blank, transfer mask and method for manufacturing semiconductor device
CN108319104B (en) * 2017-01-16 2023-05-02 Hoya株式会社 Phase shift mask blank for manufacturing display device, method for manufacturing phase shift mask for manufacturing display device, and method for manufacturing display device
KR102568807B1 (en) * 2017-03-28 2023-08-21 호야 가부시키가이샤 Phase shift mask blank and method for manufacturing phase shift mask using the same, and pattern transfer method
CN108196421B (en) * 2017-12-14 2021-03-05 深圳市路维光电股份有限公司 Method for manufacturing gray-scale mask
CN109960105B (en) * 2017-12-26 2024-06-18 Hoya株式会社 Photomask blank, method for manufacturing photomask, and method for manufacturing display device
CN113539797B (en) * 2021-07-12 2023-03-24 武汉新芯集成电路制造有限公司 Semiconductor device and method for manufacturing the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1924697A (en) * 2001-11-27 2007-03-07 Hoya株式会社 Halftone phase shift mask blank, halftone phase shift mask, and manufacturing method thereof
CN101140416A (en) * 2006-04-21 2008-03-12 信越化学工业株式会社 Photomask blank

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0749410A (en) * 1993-08-06 1995-02-21 Dainippon Printing Co Ltd Gradation mask and its manufacture
JP3289606B2 (en) * 1996-07-11 2002-06-10 凸版印刷株式会社 Blank for halftone type phase shift mask and halftone type phase shift mask
JPH10161294A (en) * 1996-12-03 1998-06-19 Toppan Printing Co Ltd Halftone phase shift mask blank, halftone phase shift mask and its production
JP4951813B2 (en) * 2001-01-30 2012-06-13 凸版印刷株式会社 Blank for halftone phase shift mask
JP3645888B2 (en) * 2001-12-10 2005-05-11 Ｈｏｙａ株式会社 Halftone phase shift mask
JP3641460B2 (en) * 2002-02-22 2005-04-20 Ｈｏｙａ株式会社 Halftone phase shift mask blank and halftone phase shift mask
JP4459523B2 (en) * 2002-04-25 2010-04-28 Ｈｏｙａ株式会社 Halftone phase shift mask blank and halftone phase shift mask
JP3645882B2 (en) * 2002-03-01 2005-05-11 Ｈｏｙａ株式会社 Method for manufacturing halftone phase shift mask blank
JP2003322954A (en) * 2002-03-01 2003-11-14 Hoya Corp Halftone phase shifting mask blank and halftone phase shifting mask
JP2004004791A (en) * 2002-04-25 2004-01-08 Hoya Corp Halftone phase shift mask blank and halftone phase shift mask
JP4393290B2 (en) * 2003-06-30 2010-01-06 Ｈｏｙａ株式会社 Method for manufacturing gray tone mask and method for manufacturing thin film transistor substrate
WO2005124454A1 (en) * 2004-06-16 2005-12-29 Hoya Corporation Semitransmitting film, photomask blank, photomask, and semitransmitting film designing method
JP4407815B2 (en) * 2004-09-10 2010-02-03 信越化学工業株式会社 Photomask blank and photomask
JP4834203B2 (en) * 2005-09-30 2011-12-14 Ｈｏｙａ株式会社 Photomask blank manufacturing method and photomask manufacturing method
JP4784983B2 (en) * 2006-01-10 2011-10-05 Ｈｏｙａ株式会社 Halftone phase shift mask blank and halftone phase shift mask
JP4766518B2 (en) * 2006-03-31 2011-09-07 Ｈｏｙａ株式会社 Mask blank and photomask
JP2007304369A (en) * 2006-05-12 2007-11-22 Elpida Memory Inc Photomask

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1924697A (en) * 2001-11-27 2007-03-07 Hoya株式会社 Halftone phase shift mask blank, halftone phase shift mask, and manufacturing method thereof
CN101140416A (en) * 2006-04-21 2008-03-12 信越化学工业株式会社 Photomask blank

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JP特开2003-241363A 2003.08.27
JP特开2003-322956A 2003.11.14
JP特开2007-183453A 2007.07.19

Also Published As

Publication number Publication date
CN101650527A (en) 2010-02-17
JP4849276B2 (en) 2012-01-11
JP2010044274A (en) 2010-02-25

Similar Documents

Publication Publication Date Title
CN101650527B (en) Gray tone mask blank, gray tone mask and forming method of product machining identification or product information identification
US7618753B2 (en) Photomask blank, photomask and method for producing those
JP5799063B2 (en) Method for manufacturing transfer mask and method for manufacturing semiconductor device
JP5412507B2 (en) Mask blank and transfer mask
TWI390338B (en) Half-tone stacked film, photomask-blank, photomask and fabrication method thereof
CN102385241A (en) Photomask blank and photomask making method
JP5615488B2 (en) Method for manufacturing phase shift mask
KR20110002053A (en) Photomask blank, photomask, and method of manufacturing photomask blank
JP2000511301A (en) Decaying embedded phase-shift photomask blank
JP2020064304A (en) Photomask blank and method for manufacturing the same, method for manufacturing photomask, and method for manufacturing display device
KR101923272B1 (en) Photomask blank, making method, and photomask
JP7176843B2 (en) Phase shift mask blank for manufacturing display device, method for manufacturing phase shift mask for manufacturing display device, and method for manufacturing display device
US7598004B2 (en) Film-depositing target and preparation of phase shift mask blank
JP2021144237A (en) Phase shift mask blank and manufacturing method of pase shift mask therewith, as well as manufacturing method of display device
CN102929096B (en) Y-tone mask substrate and gray-tone mask
CN111801618A (en) Mask blank, phase shift mask and method for manufacturing semiconductor device
JP5217345B2 (en) Photomask and photomask blanks
JP2001147516A (en) Half tone type phase shift mask blank and half tone type phase shift mask
JP4831368B2 (en) Gray tone mask blank and gray tone mask
JP2021149092A (en) Photomask blank, photomask production method, and display device production method
JP2019061106A (en) Phase shift mask blank and method for manufacturing phase shift mask using the same, and method for manufacturing display device
JP2018106022A (en) Method for manufacturing photomask for manufacturing display device, and method for manufacturing display device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant