CN107085351A - Etching solution and the photomask of etched liquid processing - Google Patents
Etching solution and the photomask of etched liquid processing Download PDFInfo
- Publication number
- CN107085351A CN107085351A CN201710080816.3A CN201710080816A CN107085351A CN 107085351 A CN107085351 A CN 107085351A CN 201710080816 A CN201710080816 A CN 201710080816A CN 107085351 A CN107085351 A CN 107085351A
- Authority
- CN
- China
- Prior art keywords
- photomask
- etching solution
- film
- acid
- semi
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/80—Etching
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0041—Photosensitive materials providing an etching agent upon exposure
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/708—Construction of apparatus, e.g. environment aspects, hygiene aspects or materials
- G03F7/7095—Materials, e.g. materials for housing, stage or other support having particular properties, e.g. weight, strength, conductivity, thermal expansion coefficient
- G03F7/70958—Optical materials or coatings, e.g. with particular transmittance, reflectance or anti-reflection properties
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Epidemiology (AREA)
- Public Health (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Weting (AREA)
- Optical Filters (AREA)
Abstract
The present invention provide the light transmittance that the semi light transmitting part for controlling photomask to have exquisitely is examined in manufacture of the photoetching process with photomask etching solution, using the etching solution manufacture gray scale mask method and the gray scale mask that is manufactured by this method.Etching solution comprising the ammonium cerium (IV) of nitric acid two or the cerium of sulfuric acid four (IV) ammonium.
Description
Technical field
The etching solution processed the present invention relates to the pattern of the optical film for photomask and the light processed through the etching solution are covered
Mould.
Background technology
In recent years, in the manufacture of TFT liquid crystal display devices, gray scale mask is used to simplify manufacturing process.Generally
Photomask formed by transmittance section and light shielding part, the intensity through the exposure light of mask is essentially shading and printing opacity this 2 values,
But gray scale mask is formed by transmittance section, semi light transmitting part and light shielding part, change the intensity of the exposure light passed through from each several part, formed and hidden
Light, semi-transparent and this 3 values of transmission.Use halftoning exposure carried out using gray scale mask with 1 piece of photomask it is common many
The process of block photomask amount.
One of manufacture method as such gray scale mask, proposition uses chromium compound as photomask, semi-transparent
Portion is etched and reduce thickness to photomask part, so that the scheme (patent document 1) of transmissivity as defined in obtaining.But, as this
In the method that sample is partially etched, it is difficult to equably semi light transmitting part is etched in the whole face of photomask, therefore propose and make
The method of the photomask blank of film forming is distinguished in each layer with 2 Rotating fields using photomask and semi-transparent film.
In order to form gray scale masks more than 3 ranks, if preparing multilayer with the semi-transparent of the light transmittance being determined in advance respectively
Light film is simultaneously etched successively, then not only needs the composition and thickness of the combination setting semi-transparent film of multilayer according to required light transmittance,
Implement complicated film formation process, and there is the limitation for the film for being only capable of being formed the light transmittance being previously set before film forming.
In addition, the light transmittance of the lamination formed is substantially determined, therefore can not carry out printing opacity by each monofilm for constituting it
The fine setting of rate.In addition, the effect of the interface generation light between the semi-transparent film of stacking, therefore the light transmittance obtained as a result
Calculate to produce and need to carry out preliminary experiment etc. in advance the burden to verify.
Here, as the method for making the different gray scale mask of transmissivity, disclosing the film for setting molybdenum silicide (MoSix) film
The method (patent document 2) of thick difference.This method carries out thickness adjustment by reducing the semi-transparent film formed by MoSix, makes it
Reach desired light transmittance, it is intended to take this to form desired printing opacity for first, second small semi light transmitting part of light transmittance difference
Rate is poor.Recorded in patent document 2 compared with MoSiON and MoSiN etc., MoSix makes more to hold with the decoction adjustment thickness of alkali etc.
Easily it is finely adjusted, more effectively.On the other hand, it is relatively thin as photomask and the widely used chromium class compound film of semi-transparent film, such as
Fruit is using acid or the surface treatment method of the decoction of alkali disclosed in patent document 2, it is difficult to carry out the fine setting of thickness, Er Qiecun
The problem of lack of uniformity of thickness after the etching.Therefore, depend on how to determine the terminal for subtracting membrane process, it is difficult to institute's phase
The light transmittance of prestige is agreed.
Prior art literature
Patent document
Patent document 1:Japanese Patent Laid-Open 07-049410 publications
Patent document 2:Japanese Patent Laid-Open 2009-230126 publications
The summary of invention
The technical problems to be solved by the invention
As described previously for the light transmittance adjustment of the semi light transmitting part of photomask, it is generally desirable to can also enter in membrane process is subtracted
The accurate determination of light transmittance of row and accurately hold and subtract the film time untill reaching desired value, particularly with liquid crystal display device and have
Machine EL display devices are the display device of representative, for brightness, operating rate, power saving, resolution ratio etc., it is desirable to higher product
Matter.
In order to form the solid knot such as contact hole of use photoresist such as organic insulating film on such devices
Structure, is effectively applicable the photoetching process using photomask.The dielectric film or height phase of the particularly local part different with height
Mutually the stereochemical structure to be formed such as different multiple photonasty septs is complicated, and needs photomasks more than 3 ranks, for essence
Ground is caused to form the stereochemical structure, the management of the light transmittance of the photomask used is extremely important.
Photomasks more than particularly 4 ranks, for example, be also equipped with exposure light transmission mutually not in addition to transmittance section, light shielding part
The gray scale mask of same multiple semi light transmitting parts is considered as effectively utilizing.In order to it is respectively exquisite formed this it is multiple have it is mutual
The semi light transmitting part of different transmissivities, light transmittance control is extremely important.That is, if multiple respective light transmittances in transmittance section can not be accurate
Really formed according to design load, then can not play gratifying function in the final device such as display device.
Therefore, problem of the invention is to solve the above problems there is provided the fine setting that can carry out thickness and with for realizing
The manufacture method of the gray scale mask of the etching solution and use of the low etching speed of the homogeneous film thickness etching solution.
Solve the technical scheme that technical problem is used
During conscientiously research is repeated to solve above-mentioned problem by the present inventor, the ammonium cerium (IV) of nitric acid two is found
Or cerium (IV) ammonium of sulfuric acid four etching solution can realize the thickness fine setting of optical film in the pattern manufacturing procedure of the optical film of photomask
And homogeneous film thickness, and the ammonium cerium (IV) of nitric acid two or the cerium of sulfuric acid four (IV) ammonium are combined with acid, as a result find that more Gao Shui can be achieved
The thickness fine setting of flat existing optical film and homogeneous film thickness, after further being studied, complete the present invention.
That is, the present invention relates to herein below.
[1] etching solution processed for the pattern of the optical film of photomask, wherein, the photomask is used for more than 3 ranks
Photoetching process, includes the ammonium cerium (IV) of nitric acid two or the cerium of sulfuric acid four (IV) ammonium.
[2] etching solution as described in [1], it is characterised in that photomask has different first semi-transparent of exposure light transmission
Light portion and the second semi light transmitting part.
[3] etching solution as described in [1] or [2], wherein, also comprising acid.
[4] etching solution as described in [1]~[3], wherein, acid is selected from sulfuric acid, methanesulfonic acid, nitric acid, acetic acid and perchloric acid
It is one kind or two or more.
[5] etching solution as described in any one of [1]~[4], wherein, optical film is to include chromium and/or chromium compound
Film.
[6] etching solution as described in [5], wherein, chromium compound is selected from chromated oxide, chromium nitride, chromium nitride oxide
It is one kind or two or more with chromium oxynitride carbide.
[7] etching solution as described in any one of [1]~[6], wherein, etching speed is more than 0.1nm/ minutes
100.0nm/ minutes following.
[8] etching solution as described in any one of [1]~[6], wherein, etching speed is more than 0.1nm/ minutes
5.0nm/ minutes following.
[9] manufacture possesses the method for the gray scale mask of the transfer pattern with the different multiple regions of exposure light transmission,
Wherein, the etching solution described in any one of [1]~[8] is used to carry out pattern processing to optical film.
[10] method as described in [9], wherein, the optical film before pattern processing is photomask and/or semi-transparent film.
[11] method as described in [9] or [10], wherein, semi-transparent region have exposure light transmission be 10~70% and
Mutually different multiple semi light transmitting parts, with least 3 rank gray scales.
[12] gray scale mask, wherein, the gray scale mask passes through manufacturer's legal system described in any one of [9]~[11]
Make.
The effect of invention
If using etching solution of the present invention, with the fine setting of relatively thin and thickness it is difficult as optical film, particularly
, can answering according to desired device in the manufacture of the photomask of photomask and the widely used chromium class compound film of semi-transparent film
Miscellaneous design, controls the light transmittance for the semi light transmitting part that photomask has exquisitely.Especially in the formation process of semi light transmitting part, it can enter
Row transmissivity is determined, and required addition etching period is held exactly.
In addition, because such fine setting can be realized, the species for the photomask blank to be prepared can be limited.It is desired
Multiple devices require different exponent numbers or different transmittance values respectively in the case of, if the photomask blank to be prepared
Wide in variety, then completion time limit and cost can all produce problem, but if using by photomask produced by the present invention, then can pass through
The process that 1 piece of photomask carries out polylith photomask amount.On the other hand, if using the present invention, can limit pre-prepd
The species of photomask blank, and desired transmissivity is can tune in process, so can be carried with higher production efficiency
For a variety of display devices.
The simple declaration of accompanying drawing
Fig. 1 is the explanation figure for illustrating the first embodiment of the manufacture method of the photomask of the present invention.
Fig. 2 is that example is applicable by semi-transparent film, etch-stop film, photomask as the optical film being formed on transparency carrier
The explanation figure of the manufacture method of the gray scale mask of the lamination of composition.
Fig. 3 is the erosion of different sulfuric acid concentrations when representing the ammonium cerium (IV) of nitric acid two or the cerium of sulfuric acid four (IV) 2.0 mass % of ammonium
Carve the figure of the relation of liquid and etching speed.
Fig. 4 is the erosion of different concentration of nitric acid when representing the ammonium cerium (IV) of nitric acid two or the cerium of sulfuric acid four (IV) 2.0 mass % of ammonium
Carve the figure of the relation of liquid and etching speed.
Fig. 5 is different methanesulfonic acid concentration when representing the ammonium cerium (IV) of nitric acid two or the cerium of sulfuric acid four (IV) 2.0 mass % of ammonium
The figure of etching solution and the relation of etching speed.
Fig. 6 is the figure of the relation for the etching solution and etching speed for representing that nitric acid two ammonium cerium (IV) concentration is different.
Fig. 7 is the etching different with the cerium of sulfuric acid four (IV) ammonium concentration of the ammonium cerium (IV) of nitric acid two when representing 40 mass % of sulfuric acid
The figure of the relation of liquid and etching speed.
Fig. 8 is to represent that the evaluation substrate c that glass baseplate surface is formed to chromium oxide film respectively is used to contain the ammonium cerium of nitric acid two
(IV) processing time in the case that 2.0 mass % and the mass % of sulfuric acid 40 etching solution are etched and the relation for subtracting film amount
Figure.
The mode carried out an invention
Hereinafter, embodiments of the present invention are described in detail.
Fig. 1 is the explanation figure for illustrating the first embodiment of the manufacture method of the photomask of the present invention.
Process 1：Prepare as shown in Fig. 1 (a), form optical film on the transparent substrate, then the first etchant resist is formed on surface
Photomask base plate.Here, photomask base plate is photomask blank, but as photomask base plate or have been carried out
The substrate of a part of pattern formation.
The first etchant resist in photomask base plate is formed directly in the surface of optical film, as long as the work of the without prejudice to present invention
With effect, can also be situated between the first etchant resist and optical film has other films.Can be photomask as optical film, can also
It is semi-transparent film, can also have makes the functions such as the phase offset ormal weight (phase shift film) of exposure light.In addition, can be in film surface portion
With the anti-reflection layer for suppressing light reflection.In addition, optical film can laminated multi-layer film.For example, in Fig. 1, example optical film is shading
The situation of film.
Film build method known to sputtering method etc. can be used to carry out for the film build method of optical film.
Optical film raw material are not particularly limited.Here photomask is illustrated, as photomask raw material, can be enumerated for example
Using Cr as the photomask of main component.Preferably there is the anti-reflection layer of Cr oxides etc. in surface portion.
Process 2：Using drawing apparatus, describe the depicting pattern (the first depicting pattern) for forming transmittance section.After description,
Carry out the first development and form the first corrosion-resisting pattern (Fig. 1 (b)).Here, resist uses positive photo resist, so describing
Partial resist is removed.
Process 3：Using the first corrosion-resisting pattern formed in process 1 as etching mask, etching removes optical film (photomask)
(Fig. 1 (c)).Here, carrying out wet etching using known etching solution.Thus describe and complete transmittance section (the first pattern formation work
Sequence).
Process 4：Peel off and remove the first corrosion-resisting pattern (etchant resist) (Fig. 1 (d)).
Process 5：Newly it is coated with to form the second etchant resist (Fig. 1 (e)) on surface.
Process 6：Drawing apparatus is reused, describes the second depicting pattern, second is carried out and develops.Thus corresponding to transmittance section
It is removed partly and corresponding to the second etchant resist of the part of semi light transmitting part, forms one of the surface of transparency carrier and optical film
Divide the second corrosion-resisting pattern (Fig. 1 (f)) of exposure respectively.
Process 7：Using second corrosion-resisting pattern as mask, to the optical film of part that exposes with etching of the present invention
Liquid, which is etched, subtracts film (the second pattern formation process).It is consequently formed the semi light transmitting part with desired exposure light transmission
(Fig. 1 (g)).
The present invention relates to the etching solution that the pattern of the optical film for photomask is processed, wherein, the photomask is used for 3 ranks
Photoetching process above, includes the ammonium cerium (IV) of nitric acid two or the cerium of sulfuric acid four (IV) ammonium.
Here, etching solution refers to for being etched to the optical film, such as chromium film or the chromium compound that constitute gray scale mask
Etchant comprising the ammonium cerium (IV) of nitric acid two or the cerium of sulfuric acid four (IV) ammonium.
Above-mentioned etching solution can include acid.Acid is not particularly limited, and can enumerate such as sulfuric acid, methanesulfonic acid, nitric acid, acetic acid, high chlorine
Acid etc., from the viewpoint of the etching speed for chromium film or chromium compound film, the stability of decoction, preferably sulfuric acid, first sulphur
Acid, acetic acid and nitric acid, more preferably sulfuric acid, methanesulfonic acid and acetic acid, particularly preferably sulfuric acid and methanesulfonic acid.
The content of the ammonium cerium (IV) of nitric acid two or the cerium of sulfuric acid four (IV) ammonium used in the present invention according to acid species and chromium film or
Chromium compound film and it is different, therefore be not particularly limited, when etchant is set into 100 mass %, preferably 0.1 mass %
The mass % of~10 mass %, more preferably 0.5 mass %~8.0, further the mass % of more preferably 1.0 mass %~6.0.
On the etching speed, for having the substrate of the layer (or film) formed by chromium or chromium compound on its surface,
It is preferably that 0.1nm/ minutes above 100.0nm/ minutes are following in the thickness direction of the layer (or the film), preferably 0.1nm/ minutes
Above 10.0nm/ minutes is following, further more preferably 0.1nm/ minute above 5.0nm/ minutes below, preferably 0.3nm/ minutes
Below above 1.0nm/ minutes.
The flox condition of etching solution when temperature, time during etching, dipping and the shake condition of substrate are (also including using
Spray sparges etchant the condition of substrate) as long as optimization those skilled in the art all can suitably carry out,
Especially for temperature, preferably 20.0~25.0 DEG C.If temperature is within the above range, can at room temperature it be used in CR, temperature
Degree is stable, therefore preferably.In addition, for dip time, preferably 30.0 seconds~180.0 seconds.If dip time is in above-mentioned model
In enclosing, then from the viewpoint of the etching liquid measure needed for being readily available inner evenness in device processing and handling preferably.
Optical film refers to semi-transparent film, etch-stop film, photomask, and pattern processing refers to the figure in photomask manufacturing process
Case is processed.
Process 8：The second etched pattern is peeled off, the 3 rank photomasks with transmittance section, light shielding part, semi light transmitting part complete (Fig. 1
(h))。
In the manufacture method of photomask shown in Fig. 2, example as the optical film being formed on transparency carrier be applicable by
The manufacture method of the gray scale mask for the lamination that semi-transparent film, etch-stop film, photomask are constituted.
Process 1：Prepare to possess on the transparent substrate the light formed by the lamination of semi-transparent film, etch-stop film, photomask
Film is learned, then is formed with surface the photomask base plate (Fig. 2 (a)) of the first etchant resist.The semi-transparent film is that have through exposure light
A part defined exposure light transmission film, be 50~60% for example with exposure light transmission in present embodiment
Film.
In addition, photomask and etch-stop film have etching selectivity, it is (wet because being applicable herein by the etchant to the opposing party
Method etches and is etching solution) mutually there are corrosion proof raw material to be formed.In addition, for semi-transparent film and etch-stop film,
Formed by the mutually raw material with tolerance of the etchant to the opposing party.Photomask and semi-transparent film can mutually have etching choosing
Selecting property, also can be without etching selectivity.Therefore, the etching characteristic containing Cr is used in the raw material of this photomask and semi-transparent film
Common material.
Process 2：Using drawing apparatus, describe the depicting pattern (the first depicting pattern) for forming transmittance section.After description,
Carry out the first development and form the first corrosion-resisting pattern (Fig. 2 (b)).
Process 3：Using the first corrosion-resisting pattern formed in process 2 as etching mask, etching removes photomask (Fig. 2 (c)).
Process 4：The etchant of etch-stop film is changed to, etching removes etch-stop film (Fig. 2 (d)).
Process 5：Change etchant again, semi-transparent film is removed by the etchant etching of semi-transparent film.Then, peel off
First corrosion-resisting pattern (the first etchant resist) (Fig. 2 (e)).
Process 6：The second etchant resist (Fig. 2 (f)) is newly formed on surface.
Process 7：Drawing apparatus is reused, describes the second depicting pattern, second is carried out and develops.Thus corresponding to transmittance section
It is removed partly and corresponding to the second etchant resist of the part of semi light transmitting part (the first semi light transmitting part), forms transparency carrier and shading
The second corrosion-resisting pattern (Fig. 2 (g)) that the part on the surface of film exposes respectively.
Process 8：Using the second corrosion-resisting pattern as mask, etching removes the photomask of exposed portion.Then, etchant is changed
Etching removes etch-stop film (Fig. 2 (h)).
Process 9：Then, change etchant, the semi-transparent film exposed is etched with etching solution of the present invention and subtracted
Film (the second pattern formation process).It is consequently formed the semi light transmitting part (the first semi light transmitting part) with desired exposure light transmission
(Fig. 2 (i)).
Process 10：Peel off the second etched pattern (the second etchant resist), with transmittance section, light shielding part, semi light transmitting part 3 rank light
Mask completes (Fig. 2 (j)).
In addition, to possess in addition to transmittance section, light shielding part also have exposure light transmission mutually different 2 kinds semi-transparent for manufacture
In the case of 4 rank photomasks of the transfer pattern in portion's (first, second semi light transmitting part), one can be entered for Fig. 2 (j) photomask
Step implements following process.
Process 11：The 3rd etchant resist (Fig. 3 (k)) is newly formed on surface.
Process 12：Using drawing apparatus, describe the depicting pattern for forming additional transmittance section (the second semi light transmitting part)
(the 3rd depicting pattern), the 3rd corrosion-resisting pattern (Fig. 2 (l)) is formed by carrying out the 3rd development.
Process 13：Using the 3rd corrosion-resisting pattern as mask, etching removes photomask and etch-stop film, forms second semi-transparent
Light portion (Fig. 2 (m)).
Process 14：Peel off the 3rd etched pattern (the 3rd etchant resist), possess transmittance section, light shielding part, the first semi light transmitting part and
4 rank photomasks of the second semi light transmitting part complete (Fig. 2 (n)).
Process more than, can be formed by single semi-transparent film it is multiple with different exposure light transmissions the
First, the second semi light transmitting part.
More than, use Fig. 1~2 to be illustrated as the form of the present invention, but the present invention is not limited in these forms,
As long as not destroying The effect of invention, various forms are included.As long as in addition, not destroying the action effect of the present invention, also may be used
Change the process in above-mentioned each embodiment, or add other processes.
In addition, the address of " first ", " second " in the explanation of these embodiments is used to easily represent the suitable of process
Sequence, in the case of implementing other processes before and after them or between them, can suitably replace address.
In all these forms, etching is more preferably applicable wet etching.Particularly in the photomask of device manufacture, it is necessary to
Production is on one side in more than 300mm large-scale a variety of photomask base plates with various aspect ratios and area, therefore applicable wet method
The effect of etching is obvious.
In addition, the photomask blank of optical film and etchant resist can will be formed with as the material that sets out on transparency carrier, certainly
Also the applicable photo mask midbody for having been carried out the formation of certain pattern and other processing is as the material that sets out.
The purposes of the photomask of the present invention is not particularly limited.
For example, the so-called province PEP for being also suitable for can be used as gray scale mask (reduces what is used during manufacture display device panel
The quantity of photomask).
In addition, can be used as the three-dimensional shape for forming the structural material in display device (being formed by photoresist etc.)
Photomask.If for example, forming the photonasty sept of liquid crystal display device or the insulating barrier of display device, essence can be distinguished
Ground is caused to carry out the height control of a variety of structural materials with different height, therefore invention effect is notable.More than 4 rank gray scales
Photomask is particularly advantageous.
In addition, the present invention includes the manufacture method of display device, the manufacture method is including the use of passing through any embodiment party
The process that transfer is transferred to transfer printing body with exposure device by the photomask of formula manufacture with pattern.
As the raw material of the optical film used in the photomask of the present invention, material that can be below example.
The raw material of optical film used herein are not particularly limited, the chemical combination using Cr as main component is preferably used
Thing.For example, Cr oxide, nitride, carbide, oxynitride or oxygen nitrogen carbide can be used etc., preferably using Cr's
Oxide or oxynitride.These materials can be used alone a kind, but also two or more is applied in combination.Part as light shielding part
Thickness is preferably that can obtain enough light-proofness (optical density OD >=3, preferably OD >=4).
As semi-transparent film, between photomask, there can be etching selectivity, also can be without etching selectivity.But,
In the case of not having etching selectivity (i.e. etching characteristic is common), the excellent in efficiency on common etchant, therefore production can be used.
Therefore, it can be selected from the photomask raw material of above-mentioned middle example.In addition, when etching subtracts film, easily carrying out in addition
Etching period control untill target transmission, thickness is more preferably
Preferably etch-stop film has an etching selectivity for photomask, semi-transparent film, thus can be used selected from Ta,
Mo, W and their compound (such as oxide, nitride, oxynitride or TaSi, MoSi, WSi (metal silication species)
Or their nitride, oxynitride etc.) raw material.
Embodiment
Hereinafter, more specific description is carried out to the present invention by embodiment and comparative example, but the present invention is not by these realities
Example restriction is applied, various changes can be carried out in the range of the technological thought without departing from the present invention.
It is produced on the chromium oxide film that glass substrate forms 19nm (transmissivity 17%) and 15nm (transmissivity 35.5%) respectively
Evaluation substrate a, and prepare table 1, the etchant shown in table 2 respectively.At this moment, the crystallization of each etchant is observed
The presence or absence of separate out.
Each evaluation substrate a is cut into 2.0cm × 2.0cm, fluorescent x-ray analyzer is used before etching solution dipping
(ZSX100e) thickness of chromium oxide film is determined.
Impregnate 15~1800 seconds, enter in 25 DEG C of stirrings in the glass container for being separately added into each etchants of 80ml
1 minute ultra-pure water shower of row, is dried by nitrogen stream, obtains each evaluation substrate b.
For each evaluation substrate b, using fluorescent x-ray analyzer, the etch quantity of chromium oxide film is determined, during according to dipping
Between and etch quantity calculate etching speed (E.R.).By the result and etchant of the presence or absence of crystallization precipitation and etching speed
The concentration of composition and the composition is shown in Tables 1 and 2 in the lump.
[table 1]
In the case of using any of the ammonium cerium (IV) of nitric acid two and perchloric acid, nitric acid, sulfuric acid, acetic acid, methanesulfonic acid acid,
The etching speed as target can be obtained.On the other hand, acid is using in the case of phosphoric acid, no matter which kind of concentration separates out crystallization,
Fail to determine etching speed.
[table 2]
In the case of using any of the cerium of sulfuric acid four (IV) ammonium and nitric acid, sulfuric acid, acetic acid, methanesulfonic acid acid, it can obtain
It is used as the etching speed of target.On the other hand, in the case that acid is using perchloric acid, phosphoric acid, no matter which kind of concentration separates out crystallization,
Fail to determine etching speed.
The etching of different sulfuric acid concentrations when Fig. 3 represents the ammonium cerium (IV) of nitric acid two or the cerium of sulfuric acid four (IV) 2.0 mass % of ammonium
The figure of the relation of liquid and etching speed.Confirm that sulfuric acid concentration is bigger, the lower tendency of etching speed.
The etching of different concentration of nitric acid when Fig. 4 represents the ammonium cerium (IV) of nitric acid two or the cerium of sulfuric acid four (IV) 2.0 mass % of ammonium
The figure of the relation of liquid and etching speed.In the case of the ammonium cerium (IV) of nitric acid two, it is thus identified that concentration of nitric acid is bigger, and etching speed is lower
Tendency.On the other hand, in the case of the cerium of sulfuric acid four (IV) ammonium, in the range of concentration of nitric acid is within about 40%, it is thus identified that
Concentration of nitric acid is bigger, the bigger tendency of etching speed, in the range of concentration of nitric acid is more than 40%, the ammonium cerium (IV) of nitric acid two
In the case of, it is thus identified that concentration of nitric acid is bigger, the lower tendency of etching speed.
The erosion of different methanesulfonic acid concentration when Fig. 5 represents the ammonium cerium (IV) of nitric acid two or the cerium of sulfuric acid four (IV) 2.0 mass % of ammonium
Carve the relation of liquid and etching speed.Confirm that the concentration of methanesulfonic acid is bigger, the lower tendency of etching speed.
Fig. 6 represents the different etching solution of nitric acid two ammonium cerium (IV) concentration and the relation of etching speed.Confirm the ammonium of nitric acid two
The concentration of cerium (IV) is smaller, the lower tendency of etching speed.
The ammonium cerium (IV) of nitric acid two when Fig. 7 represents 40 mass % of the sulfuric acid etching solution different with the cerium of sulfuric acid four (IV) ammonium concentration
With the relation of etching speed.Confirm that the concentration of the ammonium cerium (IV) of nitric acid two and the cerium of sulfuric acid four (IV) ammonium is bigger, etching speed is higher
Tendency.
Fig. 8 represents that the evaluation substrate c that glass baseplate surface is formed to chromium oxide film respectively is used and contains the ammonium cerium (IV) of nitric acid two
2.0 mass % and the mass % of sulfuric acid 40 etching solution be etched in the case of processing time and subtract the relation of film amount.Confirm
Linearly occur relative to processing time film reduction, therefore the transmissivity of chromium oxide can be controlled by processing time.
Claims (12)
1. the etching solution of the pattern processing for the optical film of photomask, wherein, the photoetching that the photomask is used for more than 3 ranks
Method, includes the ammonium cerium (IV) of nitric acid two or the cerium of sulfuric acid four (IV) ammonium.
2. etching solution as claimed in claim 1, it is characterised in that it is first semi-transparent that photomask has exposure light transmission different
Light portion and the second semi light transmitting part.
3. etching solution as claimed in claim 1 or 2, wherein, also comprising acid.
4. etching solution as claimed in claim 3, wherein, acid is a kind selected from sulfuric acid, methanesulfonic acid, nitric acid, acetic acid and perchloric acid
Or two or more.
5. the etching solution as described in any one of Claims 1 to 4, wherein, optical film is comprising chromium and/or chromium compound
Film.
6. etching solution as claimed in claim 5, wherein, chromium compound is selected from chromated oxide, chromium nitride, chromium nitride oxide
It is one kind or two or more with chromium oxynitride carbide.
7. the etching solution as described in any one of claim 1~6, wherein, etching speed is more than 0.1nm/ minutes
100.0nm/ minutes following.
8. the etching solution as described in any one of claim 1~6, wherein, etching speed is more than 0.1nm/ minutes
5.0nm/ minutes following.
9. the method that manufacture possesses the gray scale mask of the transfer pattern with the different multiple regions of exposure light transmission, wherein,
Etching solution described in usage right requirement any one of 1~8 carries out pattern processing to optical film.
10. method as claimed in claim 9, wherein, the optical film before pattern processing is photomask and/or semi-transparent film.
11. the method as described in claim 9 or 10, wherein, the exposure light transmission with semi-transparent region is 10~70%
And mutually different multiple semi light transmitting parts, with least 3 rank gray scales.
12. gray scale mask, wherein, the gray scale mask is manufactured by the manufacture method described in any one of claim 9~11.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016026232A JP6761255B2 (en) | 2016-02-15 | 2016-02-15 | Etching solution and photomask processed by etching solution |
| JP2016-026232 | 2016-12-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107085351A true CN107085351A (en) | 2017-08-22 |
| CN107085351B CN107085351B (en) | 2022-05-31 |
Family
ID=59615260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710080816.3A Active CN107085351B (en) | 2016-02-15 | 2017-02-15 | Etching solution and photomask processed by etching solution |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6761255B2 (en) |
| KR (1) | KR20170095747A (en) |
| CN (1) | CN107085351B (en) |
| TW (1) | TWI718249B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3951547A (en) * | 1971-05-24 | 1976-04-20 | Ulvac Corporation | Chromium oxide photomask material and the production thereof |
| US20030051740A1 (en) * | 1998-10-23 | 2003-03-20 | Chao Virginia Chi-Chuen | Method of inhibiting contaminants using dilute acid rinse |
| US20040161674A1 (en) * | 2000-12-19 | 2004-08-19 | Hoya Corporation | Graytone mask and method thereof |
| US20110123912A1 (en) * | 2004-06-22 | 2011-05-26 | Hoya Corporation | Manufacturing method of transparent substrate for mask blanks, manufacturing method of mask blanks, manufacturing method of exposure masks, manufacturing method of semiconductor devices, manufacturing method of liquid crystal display devices, and defect correction method of exposure masks |
| CN102372424A (en) * | 2010-08-12 | 2012-03-14 | Hoya株式会社 | Substrate for masking base, masking base and method for manufacturing transferring mask |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW275671B (en) * | 1994-11-16 | 1996-05-11 | United Microelectronics Corp | Manufacturing method for half-tone phase shifting mask |
| TW390975B (en) * | 1999-09-14 | 2000-05-21 | Taiwan Semiconductor Mfg | Method of fabricating high transparency phase-shift-decaying mask |
| JP3749204B2 (en) * | 2002-07-16 | 2006-02-22 | 林純薬工業株式会社 | Method for recovering cerium from chromium etchant |
| KR100848815B1 (en) * | 2004-11-08 | 2008-07-28 | 엘지마이크론 주식회사 | Half tone mask and fabricating method and flat panel displayq |
| TWI395053B (en) * | 2005-02-28 | 2013-05-01 | Hoya Corp | Gray level mask, and gray level mask blank |
| JP5433925B2 (en) * | 2006-02-23 | 2014-03-05 | 大日本印刷株式会社 | Mask blank and gradation mask |
| JP5407125B2 (en) * | 2007-08-29 | 2014-02-05 | 大日本印刷株式会社 | Gradation mask |
| US8216745B2 (en) * | 2007-11-01 | 2012-07-10 | Ulvac Coating Corporation | Half-tone mask, half-tone mask blank and method for manufacturing half-tone mask |
| JP2014115675A (en) * | 2014-02-17 | 2014-06-26 | Hoya Corp | Multilevel gradation photomask for manufacturing display device, method for manufacturing multilevel gradation photomask for manufacturing display device, and method for manufacturing display device |
-
2016
- 2016-02-15 JP JP2016026232A patent/JP6761255B2/en active Active
-
2017
- 2017-02-14 KR KR1020170020040A patent/KR20170095747A/en not_active Application Discontinuation
- 2017-02-15 CN CN201710080816.3A patent/CN107085351B/en active Active
- 2017-02-15 TW TW106104892A patent/TWI718249B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3951547A (en) * | 1971-05-24 | 1976-04-20 | Ulvac Corporation | Chromium oxide photomask material and the production thereof |
| US20030051740A1 (en) * | 1998-10-23 | 2003-03-20 | Chao Virginia Chi-Chuen | Method of inhibiting contaminants using dilute acid rinse |
| US20040161674A1 (en) * | 2000-12-19 | 2004-08-19 | Hoya Corporation | Graytone mask and method thereof |
| US20110123912A1 (en) * | 2004-06-22 | 2011-05-26 | Hoya Corporation | Manufacturing method of transparent substrate for mask blanks, manufacturing method of mask blanks, manufacturing method of exposure masks, manufacturing method of semiconductor devices, manufacturing method of liquid crystal display devices, and defect correction method of exposure masks |
| CN102372424A (en) * | 2010-08-12 | 2012-03-14 | Hoya株式会社 | Substrate for masking base, masking base and method for manufacturing transferring mask |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2017146365A (en) | 2017-08-24 |
| TWI718249B (en) | 2021-02-11 |
| JP6761255B2 (en) | 2020-09-23 |
| CN107085351B (en) | 2022-05-31 |
| KR20170095747A (en) | 2017-08-23 |
| TW201741442A (en) | 2017-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102297223B1 (en) | Phase shift mask blank and manufacturing method therefor, phase shift mask and manufacturing method therefor, and display device manufacturing method | |
| CN100593755C (en) | Phase-shift photomask-blank, phase-shift photomask and fabrication method thereof | |
| EP2983044B1 (en) | Halftone phase shift photomask blank and making method | |
| JP3064769B2 (en) | PHASE SHIFT MASK, ITS MANUFACTURING METHOD, AND EXPOSURE METHOD USING THE PHASE SHIFT MASK | |
| US9494852B2 (en) | Mask blank and method of manufacturing phase shift mask | |
| KR101374484B1 (en) | Photomask blank, process for production of photomask, and chromium-containing material film | |
| KR20010024372A (en) | Photomask blank, photomask, methods of manufacturing the same, and method of forming micropattern | |
| KR100510309B1 (en) | Phase shifter film and production method therefor | |
| US20160291455A1 (en) | Method for preparing halftone phase shift photomask blank | |
| JP2017182052A (en) | Manufacturing method of phase shift mask blank, phase shift mask, and display device | |
| CN103376642A (en) | Photomask blank and manufacturing method thereof | |
| KR102243226B1 (en) | Halftone phase shift photomask blank, making method, and halftone phase shift photomask | |
| EP1286217A2 (en) | Phase shift mask blanks, their manufacture and use | |
| US20030025216A1 (en) | Phase shift mask blank, phase shift mask, and method of manufacture | |
| KR102181325B1 (en) | Binary photomask blank, preparation thereof, and preparation of binary photomask | |
| CN109782525A (en) | Mask substrate and its manufacturing method, phase shifting mask and its manufacturing method | |
| US8647795B2 (en) | Sputtering target material, silicon-containing film forming method, and photomask blank | |
| DE10349087B4 (en) | Method of making halftone phase shift mask blanks | |
| CN107229181A (en) | The manufacture method of phase shifting mask blanket, phase shifting mask and display device | |
| CN109782526A (en) | Mask blank and its manufacturing method, half-tone mask and its manufacturing method | |
| CN105717738A (en) | Method of producing photomask and method of producing display apparatus | |
| JPH05297570A (en) | Production of photomask blank | |
| CN107085351A (en) | Etching solution and the photomask of etched liquid processing | |
| KR20160031423A (en) | Photomask blank | |
| JP5217345B2 (en) | Photomask and photomask blanks |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |