CN103442868A - Method for cleaning mold with mold-releasing layer and method for producing mold with mold-releasing layer - Google Patents
Method for cleaning mold with mold-releasing layer and method for producing mold with mold-releasing layer Download PDFInfo
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- CN103442868A CN103442868A CN2012800135807A CN201280013580A CN103442868A CN 103442868 A CN103442868 A CN 103442868A CN 2012800135807 A CN2012800135807 A CN 2012800135807A CN 201280013580 A CN201280013580 A CN 201280013580A CN 103442868 A CN103442868 A CN 103442868A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/70—Maintenance
- B29C33/72—Cleaning
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
- B08B7/0035—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by radiant energy, e.g. UV, laser, light beam or the like
- B08B7/0057—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by radiant energy, e.g. UV, laser, light beam or the like by ultraviolet radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/58—Applying the releasing agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
- B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
- B29C37/0067—Using separating agents during or after moulding; Applying separating agents on preforms or articles, e.g. to prevent sticking to each other
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
A method for cleaning a mold with a mold-releasing layer, said mold being obtained by providing a mold (30), which is used for the purpose of transferring a predetermined pattern to a transfer-receiving object by imprinting, with a mold-releasing layer (31). The mold-releasing layer (31) is formed of a fluorine compound. The method for cleaning a mold with a mold-releasing layer comprises: an ultraviolet light irradiation step wherein the mold-releasing layer (31) of the mold with a mold-releasing layer is irradiated with ultraviolet light; and a cleaning step wherein the mold-releasing layer, which has been chemically modified by the ultraviolet light irradiation step, is cleaned and removed. In the ultraviolet light irradiation step, the cumulative irradiation energy of ultraviolet light is set to 5,000-7,000 mJ/cm2 when the center wavelength of the ultraviolet light source is 150-200 nm.
Description
Technical field
The present invention relates to the cleaning method of the mould of release layer with the manufacture method of the mould of release layer.
Background technology
In the past, for the disk used in hard disk etc., thereby used magnetic head width minimization, make to narrow down and realize the method that densification is such between the data track of recorded information always.
On the other hand, for such disk, growing along with densification, start to ignore the magnetic influence between adjacent track.Therefore, existing method has reached the limit aspect densification.
Therefore, proposed a kind of novel medium, it is the patterned media formed by the data track Magnetic Isolation by disk.Such patterned media refers to, want to remove (groove processing) by the magnetic material of unwanted part in recording thus improve the medium of signal quality.
Volume production technology as this patterned media; known have a following described stamping technique (imprint) (or being called nanometer embossing); in this technology; the relief pattern that master mold or backed stamper (also referred to as work backed stamper (working replica)) are had is transferred to and is transferred on material to come thus fabricating patterned medium, described backed stamper is to using master mold to copy and obtain as the grand master pattern mould and by carrying out transfer printing more than 1 time or 2 times.
It should be noted that, this stamping technique roughly is divided into 2 kinds, has hot padding and optical pressure and prints.
Hot padding refers to method as described below: the mould that in heating, will be formed with the micro concavo-convex pattern is attached to as on by the thermoplastic resin of moulding material, to by moulding material, being carried out cooling/demoulding, carries out thus the transfer printing of fine pattern afterwards.
In addition, optical pressure prints and to refer to method as described below: the mould that will be formed with the micro concavo-convex pattern be attached to as on the light-cured resin by moulding material then irradiating ultraviolet light it is solidified, to by moulding material, being carried out the demoulding, carry out thus the transfer printing of fine pattern afterwards.
Based on the impression the operation of the volume production by article shaped in, usually can not use master mold itself.Particularly, as the alternative mould of master mold, in every volume production production line, use be called as the mould of work backed stamper, by the duplicated backed stamper of master mold.Backed stamper be by the micro concavo-convex pattern transfer of master mold to other by moulding material and duplicated secondary mould or the micro concavo-convex pattern of this secondary mould further is transferred to other by moulding material and duplicated three moulds; Etc..
Therefore, even backed stamper produces distortion or breakage occurs in the volume production operation of impression, to master mold, can not impact yet.That is, as long as master mold is had nothing to do, can produce any amount of backed stamper, bring interference therefore can to the volume production operation of impression.
In addition, as mentioned above, when making this backed stamper, the secondary mould for three moulds etc. needs to be formed with the master mold of micro concavo-convex pattern or as the backed stamper of grand master pattern, (it should be noted that, below, for convenience of explanation, will be called the grand master pattern mould as these moulds of the benchmark that forms backed stamper) be attached to be transferred in thing by moulding material, following need to be by the grand master pattern mould from by moulding material and be transferred thing and break away from this.
In addition, in the volume production operation of impression, need similarly backed stamper is attached in being transferred thing by moulding material on, following need to be by backed stamper from by moulding material and be transferred thing and break away from and (it should be noted that in this, below, for convenience of explanation, grand master pattern mould, backed stamper only are called to mould).
In order to make mould successfully demoulding from being transferred thing, known have apply in advance releasing agent form release layer and then carry out the transfer printing of pattern on die surface.
Release layer so is set on mould, thereby can improves mould and be transferred the release property between thing.
For example, in patent documentation 1, record, the surface modifier that use consists of the organo-silicon compound with straight chain perfluoropolyether structures is as the technology of mold release compositions.
In addition, in patent documentation 2, put down in writing as the silicone-based releasing agent of basic structure for usining the organopolysiloxane structure, particularly, can enumerate unmodified or modified silicon oil, the polysiloxanes that contains trimethyl silicane alcoxyl base silicic acid, silicone-based acrylic resin etc.
In addition, be arranged at release layer as above on mould and will inevitably subtract consumption due to impression repeatedly, therefore cause implementing well the demoulding, in the poorest situation, likely cause the transfer printing defect.In addition, because release layer subtracts consumption, can't implement well in the situation of the demoulding, also likely can cause that forming the residue by moulding material that is transferred thing is attached to mold fouling such on mould.
Therefore, for the mould that is provided with release layer, generally can implement the regeneration processing to having implemented the to a certain degree mould of the impression of number of times.Process as concrete regeneration, at first, utilize the sulfuric acid that mixes sulfuric acid and hydrogen peroxide and obtain and the mixed liquor of hydrogen peroxide etc. to be cleaned thus release layer is removed from mould the mould with release layer.Afterwards, suitably implement to clean and dry etc., and again releasing agent is coated on mould new release layer is set thus, thereby the regeneration that completes mould is processed.
It should be noted that, in patent documentation 3, in order to remove the photoresist layer remained on pressing mold, implemented successively aqueous alkali processing, solvent processing, UV/O
3processing, Pure water preparation, remove the remaining photoresist layer on pressing mold thus.That is, thus the thinking in patent documentation 3 be in order to remove resist, utilize ozone come oxidation of organic compounds make its alkaline soluble in.
The prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application Publication 2008-537557 communique
Patent documentation 2: TOHKEMY 2010-006870 communique
Patent documentation 3: Japanese kokai publication hei 10-92024 communique
Summary of the invention
Invent problem to be solved
As described in patent documentation 1 and 2, usually use per-fluoro polyether compound or silicon based compound as the nano impression releasing agent.
These compounds are usually due to fluorine or silicon and can improve with respect to the release property that is transferred thing.Particularly, in the strand of compound, be not provided with the modified silicon alkyl part, be that the described part that contains fluorine-based or silicon makes the surface free energy that is transferred thing contact predetermined portions of mould reduce.
Consequently, can the successfully disengaging of the release layer from being arranged on mould by mould.Therefore, for good release layer is set, consider preferably to make and the surface free energy reduction that is transferred thing and contact predetermined portions.
For the mould that the state that the above-mentioned such surface free energy of release layer that surface free energy is reduced is larger for example is not set, utilize the mixed liquor of sulfuric acid and hydrogen peroxide or IPA (isopropyl alcohol), pure water to implement, in the situation of cleaning treatment, can carry out well cleaning treatment.
But, in order to realize the demoulding smoothly, make in the situation that be provided with on mould the release layer reduced with the surface free energy that is transferred thing and contacts the reservations office, due to the impact of the extremely low surface free energy of this release layer, can cause the such cleaning solvent of the mixed liquor of sulfuric acid and hydrogen peroxide or IPA and pure water, clean material and form the state of non-constant with respect to the wetability of release layer.
So, if wetability is poor,, in the situation that mould when regeneration implements to clean, there are the following problems: can bring out and clean trace, uneven drying etc., hinder good mould regeneration.Therefore in addition, if wetability is poor, with the reduction of cleaning efficiency, also be closely related, in the volume production operation of patterned media etc., at the process aspect of the transfer printing that is attended by fine pattern, can produce very large problem.
Therefore, the present application proposes in order to address the above problem, the manufacture method that it provides a kind of cleaning method of the mould with release layer and has the mould of release layer, wherein, can be cleaned according to the mode of almost completely removing the release layer formed on mould, and can not be made to carry out mould regeneration under the deteriorated condition of submicroscopic patterns.
Solve the means of problem
The 1st mode of the present invention is a kind of cleaning method of the mould with release layer,
Above-mentioned with in the mould of release layer, for by impression, predetermined pattern transfer being provided with to release layer to the mould that is transferred thing,
Above-mentioned cleaning method is characterised in that,
Above-mentioned release layer consists of fluorine compounds,
Above-mentioned cleaning method possesses:
Ultraviolet ray treatment with irradiation operation, wherein, to the release layer irradiation ultraviolet radiation of the above-mentioned mould with release layer; With
The cleaning treatment operation, wherein, thereby cleaned and be removed the release layer that the chemistry modification occurs because of above-mentioned ultraviolet treatment with irradiation operation.
Wherein, in above-mentioned ultraviolet treatment with irradiation operation, when the centre wavelength of ultraviolet light source output is made as 150nm～200nm, ultraviolet cumulative exposure energy is 5000mJ/cm
2～7000mJ/cm
2.
The 2nd mode of the present invention is the cleaning method of the described mould with release layer of above-mentioned the 1st mode, it is characterized in that,
Above-mentioned fluorine compounds are following compound,
[changing 1]
Wherein, m is natural number.
The 3rd mode of the present invention is the cleaning method of the described mould with release layer of above-mentioned the 1st mode, it is characterized in that,
Above-mentioned fluorine compounds are following compound,
[changing 2]
Wherein, m is natural number.
The 4th mode of the present invention is the manufacture method of the described mould with release layer of above-mentioned the 1st mode, it is characterized in that,
Its combination has: above-mentioned release layer is heated to the heat treated of the predetermined condition of high temperature and above-mentioned release layer is irradiated at least any one operation in the electron ray treatment with irradiation of electron ray; With above-mentioned ultraviolet treatment with irradiation operation.
The 5th mode of the present invention is a kind of manufacture method of the mould with release layer, it is characterized in that,
Use described any cleaning method with the mould of release layer of above-mentioned the 1st～4th mode to be cleaned and be removed the release layer of mould, and release layer is set again removing on the mould of release layer.
The invention effect
According to the present invention, can be cleaned according to the mode of almost completely removing the release layer formed on mould, and can not be made to carry out mould regeneration under the deteriorated condition of submicroscopic patterns.
The accompanying drawing explanation
Fig. 1 is the schematic sectional view described for the mould with release layer to present embodiment.
Fig. 2 is the figure that the measurement result based on XPS (x-ray photoelectron light splitting) of fluorine in embodiment is shown.
The specific embodiment
Below embodiments of the present invention are described.Fig. 1 (a) illustrates the grand master pattern mould or by the schematic sectional view of the appearance of the backed stamper of grand master pattern Mold Making.It should be noted that, in the present embodiment, by the grand master pattern mould (being master mold etc.) of impression use or by the backed stamper of grand master pattern Mold Making referred to as mould.
As the material of mould 30, so long as can as the material of impressing mould any material all can.For example, implement, in the situation of optical pressure seal, if there is the material (such as quartz, sapphire etc.) of light transmission, can be exposed across mould 30, therefore preferably.In addition, as the material of mould 30, can also use silicon wafer, nickel etc.Further, in the situation that implement hot padding, also can use SiC substrate etc.
It should be noted that, the predetermined pattern formed on this mould 30 can be the micron number magnitude, but, from the performance this respect consideration of e-machine in recent years, can be also nanometer scale; The performance of the end article of making, preferably nanometer scale if consider by impressing mould etc.
(setting of release layer on mould)
Fig. 1 (b) is illustrated in the schematic sectional view that is provided with the appearance of release layer 31 on mould 30.As shown in Fig. 1 (b), in mould 30, at least at the part coating releasing agent that is formed with predetermined pattern, release layer 31 is set thus.
Make such mould that is provided with release layer 31 30 and be transferred thing and contact and carry out thus the transfer printing predetermined pattern.In addition, corresponding each method for stamping (optical pressure prints or hot padding) makes to be transferred thing and solidifies.Then, the mould 30 that is provided with release layer 31 is peeled off from the thing that is transferred solidified, thereby, because the surface free energy that is provided with release layer 31 moulds 30 reduces, therefore can easily be peeled off.
So, by release layer 31 is set on mould 30, thereby can successfully mould 30 be separated from being transferred thing, therefore can when improving production capacity (throughput), suppress mould 30 and the breaking-up that is transferred the pattern of thing.
The releasing agent be coated with on mould 30, be in release layer 31, use fluorine compounds.So, if highly stable fluorine compounds are for release layer 31 by chemistry, can make well to reduce with the surface free energy that is transferred the mould 30 that thing contact, so can realize the very good demoulding.
In addition, if use such mould that is provided with release layer 31 30, be transferred the transfer printing of repeatedly carrying out predetermined pattern on thing, due to the generation that subtracts consumption etc. of release layer 31, can causing carrying out well the demoulding or produce a part that is transferred thing being attached to pollution such on mould 30 etc.Therefore, for fear of such problem and in the situation that the enforcement multi-impression, once remove release layer 31 set on mould 30, needs the regeneration that the such mould of new release layer 31 30 is set to process.
(regeneration about mould is processed)
In order as mentioned above mould 30 to be carried out to high-quality regeneration, the inventor draws following technological thought: the chemistry modifications occur the lip-deep release layer 31 that makes to be formed at this mould 30 is that effectively described release layer 31 fluorine compounds highly stable by chemistry form.
Particularly, in the leading portion that utilizes as in the past the mixed liquor etc. of sulfuric acid and hydrogen peroxide to be cleaned, as the modification of carrying out for release layer 31, implement the UV treatment to release layer 31 irradiation ultraviolet radiations.Herein, for ultraviolet treatment with irradiation, according to the cumulative exposure energy, be preferably 5000mJ/cm
2～7000mJ/cm
2the mode ultraviolet ray that is 150nm～200nm to the centre wavelength of release layer 31 irradiation ultraviolet radiation light sources outputs.It should be noted that, can will be heated to the heat treated of the predetermined condition of high temperature to release layer 31 and any one or two kinds of and above-mentioned ultraviolet treatment with irradiation combination in the electron ray treatment with irradiation of release layer 31 irradiation electron raies be implemented.In addition, except said method, as long as can make release layer 31 that the chemistry modification occurs, can be any processing.
The releasing agent molecule of release layer 31 decomposes thus, and the surface free energy of mould 30 own improves.Afterwards, thereby utilize the mixed liquor, IPA/ pure water etc. of sulfuric acid and hydrogen peroxide to be cleaned mould 30, remove release layer 31, and suitably cleaned or dry etc.In addition, thereby by again being coated with releasing agent, new release layer 30 is set on mould 30 again, realizes thus regeneration.
The effect of<embodiments of the present invention >
In present embodiment as above, can obtain following effect.In the regeneration of mould is processed, the release layer 31 formed for the fluorine compounds highly stable by chemistry, at first carry out the chemistry modification, make thus the releasing agent molecular breakdown, therefore after matting in can easily remove the releasing agent that is used to form release layer 31.
Thus, only utilize the cleaning based on existing cleaning method, just can almost completely remove the release layer 31 that can't remove, therefore can realize high-quality cleaning.Therefore, the regeneration that can successfully implement mould 30 is processed thus and can be realized the impression processing with high efficiency.Further, even used mould 30 also can, fully having reduced under the deteriorated state of pattern mould 30 processing of regenerating, therefore can make the life-span of mould 30 elongated.Therefore, particularly, for the expensive mould of the transfer printing of carrying out submicroscopic patterns, the life-span of recycling can be extended, therefore significantly cost cutting can be realized.
Such mould all can be used in hot padding and optical pressure India and China, further also can be applied in nanometer embossing.In the patterned media that particularly present embodiment suitably can be applied to use stamping technique and make.
More than enumerated embodiments of the present invention, above-mentioned disclosure is for exemplary embodiment of the present invention is shown.Scope of the present invention is not limited to above-mentioned illustrative embodiments.Those skilled in the art no matter in this specification, whether clear and definite record or hint arranged, if can append various changes to embodiments of the present invention based on the disclosure of the specification and implement.
Embodiment
Embodiment then is shown to be specifically described the present invention.The present invention is not limited to following examples, and this is from needn't.
<embodiment 1 >
In the present embodiment, use the mould 30 formed by quartz base plate, be provided with the line width patterns (line-and-space pattern) of the half spacing 25nm periodic structure of degree of depth 30nm, line length 15nm and interval 10nm on described quartz base plate.By in this mould 30 releasing agent that contains following compound (identical with above-mentioned [changing 1]) that to impregnated in VERTRELXF-UP (VERTREL is registration mark, DuPont-Mitsui Fluorochemicals Co., Ltd. manufacture) dilution be 0.5wt% 5 minutes.Wherein, m is natural number.
[changing 3]
The speed of dividing with 120mm/ afterwards, draws high mould 30.
So utilize infusion process to carry out the coating of releasing agent.It should be noted that, now with the temperature of 170 ℃, sample has been carried out to heat treatment.Afterwards, mould 30 has been carried out to the rinsing processing.Now use VERTRELXF-UP as rinsing liquid, carry out rinsing in 10 minutes and process.So obtained the mould with release layer.
For such mould with release layer, irradiating 2 minutes centre wavelength is that 172nm, (lamp) power output are 50mW/cm
2ultraviolet ray.It should be noted that, irradiation environment now is N
2with O
2mixed atmosphere, the scope of its flow-rate ratio is to make O
2be 5%～10%.In addition, after irradiation ultraviolet radiation, utilize hot sulfuric acid, cold sulfuric acid to carry out respectively 30 minutes cleaning treatment, further utilize pure water, IPA to carry out cleaning treatment.
In Fig. 2, use x-ray photoelectron light splitting (XPS) to observe the F1s power spectrum of fluorine.As shown in Figure 2, almost can't observe the F1s peak, therefore think that the releasing agent that forms release layer almost is completely removed.
<embodiment 2 >
In the present embodiment, except the releasing agent that use contains following compound (identical with above-mentioned [changing 2]), carry out similarly to Example 1.F1s power spectrum to fluorine is observed, and result in the same manner as in Example 1, almost can't be observed the F1s peak.Wherein, m is natural number.
[changing 4]
<comparative example >
In comparative example, prepare 3 moulds with release layer of making to obtain according to the method identical with embodiment, to irradiating ultraviolet time dependence, be studied specifically.The 1st is exemplified as fully the not situation of irradiation ultraviolet radiation; The 2nd example is the situation of 5 minutes that irradiation time is made as; The 3rd example is the situation of 10 minutes that irradiation time is made as.No matter any situation, all similarly utilize hot sulfuric acid, cold sulfuric acid to carry out respectively 30 minutes cleaning treatment with embodiment, further utilizes pure water, IPA to carry out cleaning treatment.
As shown in Figure 2, not under the 1st sample situation of irradiation ultraviolet radiation and applicable existing cleaning method, the F1s power spectrum of fluorine demonstrates high value fully, and known releasing agent is not removed.In addition, also can confirm the peak of the F1s power spectrum of fluorine in the situation of the 2nd example, the 3rd example, therefore the cleaning of known arbitrary situation bottom knockout agent is all insufficient.
<estimate
Known according to embodiment, comparative example, for make the modification of release layer chemistry processing, be ultraviolet irradiation life period dependence, known to utilize ultraviolet ray and the irradiation time that centre wavelength is 172nm be 2 minutes, shows very high effect for removing releasing agent.
Think this be due to, in the fluorine based polymer that functional group is hydroxyl endways, by ultraviolet treatment with irradiation, make the cut-out of main chain from connecing subterminal part, molecule starts to decompose at leisure.If infer thus, irradiation ultraviolet radiation surpasses 2 minutes, and main chain is whole decomposes, and the fluorine low molecular compound therefore generated has carried out chemical sex modification to die surface.
Therefore, even infer that imposing predetermined cleaning treatment after having implemented irradiation ultraviolet radiation also can't remove releasing agent well.With respect to this, irradiate about 2 minutes in ultraviolet situation, only think endways near, adsorb near the cut-out that produces molecule base, therefore by after predetermined cleaning treatment can remove well releasing agent.
According to above content, the optimum condition in ultraviolet treatment with irradiation is studied.The power output of having irradiated 2 minutes in the above-described embodiment, is 50mW/cm
2ultraviolet ray, therefore ultraviolet cumulative exposure energy is obtained as follows.
50mW/cm
2×120sec=6000mJ/cm
2
Think thus, in the scope that the centre wavelength of exporting at ultraviolet light source is 150nm～200nm, making the cumulative exposure energy is 5000mJ/cm
2～7000mJ/cm
2scope, produce thus effect same as the previously described embodiments.
The explanation of symbol
30 moulds
31 release layers
Claims (5)
1. the cleaning method with the mould of release layer, described with in the mould of release layer, and for by impression, predetermined pattern transfer being provided with to release layer to the mould that is transferred thing, described cleaning method is characterised in that,
Described release layer consists of fluorine compounds,
Described cleaning method possesses:
Ultraviolet ray treatment with irradiation operation, wherein, to the release layer irradiation ultraviolet radiation of the described mould with release layer; With
The cleaning treatment operation, wherein, thereby cleaned and be removed the release layer that the chemistry modification occurs because of described ultraviolet treatment with irradiation operation;
Wherein, in described ultraviolet treatment with irradiation operation, when the centre wavelength of ultraviolet light source output is made as 150nm～200nm, ultraviolet cumulative exposure energy is 5000mJ/cm
2～7000mJ/cm
2.
2. the cleaning method of the mould with release layer as claimed in claim 1, is characterized in that,
Described fluorine compounds are following compound,
Wherein, m is natural number.
3. the cleaning method of the mould with release layer as claimed in claim 1, is characterized in that,
Described fluorine compounds are following compound,
Wherein, m is natural number.
4. the cleaning method of the mould with release layer as claimed in claim 1, is characterized in that,
Its combination has: described release layer is heated to the heat treated of the predetermined condition of high temperature and described release layer is irradiated at least any one operation in the electron ray treatment with irradiation of electron ray; With described ultraviolet treatment with irradiation operation.
5. the manufacture method with the mould of release layer, is characterized in that,
Right to use requires 1～any cleaning method with the mould of release layer claimed in claim 4 to be cleaned and be removed the release layer of mould, and release layer is set again removing on the mould of release layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-099344 | 2011-04-27 | ||
| JP2011099344 | 2011-04-27 | ||
| PCT/JP2012/060946 WO2012147728A1 (en) | 2011-04-27 | 2012-04-24 | Method for cleaning mold with mold-releasing layer and method for producing mold with mold-releasing layer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103442868A true CN103442868A (en) | 2013-12-11 |
Family
ID=47072246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012800135807A Pending CN103442868A (en) | 2011-04-27 | 2012-04-24 | Method for cleaning mold with mold-releasing layer and method for producing mold with mold-releasing layer |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2012147728A1 (en) |
| KR (1) | KR20140021644A (en) |
| CN (1) | CN103442868A (en) |
| WO (1) | WO2012147728A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169690A (en) * | 1994-10-21 | 1998-01-07 | 大金工业株式会社 | Release agent, hardened skin-film obtained from said release agent and forming method using said release agent |
| US6808379B2 (en) * | 2001-05-10 | 2004-10-26 | Samsung Electronics Co., Ltd. | Cleaner for molding apparatus of semiconductor chip packages |
| CN101060995A (en) * | 2004-11-24 | 2007-10-24 | 分子制模股份有限公司 | Method and composition providing desirable characteristics between a mold and a polymerizable composition |
| CN101795838A (en) * | 2007-09-06 | 2010-08-04 | 3M创新有限公司 | Form the method for mould and use described mould to form the method for goods |
| TW201100242A (en) * | 2009-06-19 | 2011-01-01 | Tokyo Electron Ltd | Imprint system, imprint method, program and computer recording medium |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100254839B1 (en) * | 1993-11-22 | 2000-05-01 | 이노우에 노리유끼 | Mold-release agent, cured coating film prepared therfrom, and method of molding with said agent |
| JP2011009362A (en) * | 2009-06-24 | 2011-01-13 | Tokyo Electron Ltd | Imprint system, imprinting method, program, and computer storage medium |
| JP5798349B2 (en) * | 2010-03-30 | 2015-10-21 | Hoya株式会社 | Mold with release layer, method for producing the same, and method for producing the mold |
| JP5019009B2 (en) * | 2010-10-29 | 2012-09-05 | 大日本印刷株式会社 | IMPRINT MOLD CLEANING METHOD, CLEANING DEVICE, AND IMPRINT MOLD MANUFACTURING METHOD |
-
2012
- 2012-04-24 CN CN2012800135807A patent/CN103442868A/en active Pending
- 2012-04-24 WO PCT/JP2012/060946 patent/WO2012147728A1/en active Application Filing
- 2012-04-24 JP JP2013512369A patent/JPWO2012147728A1/en active Pending
- 2012-04-24 KR KR1020137029020A patent/KR20140021644A/en not_active Application Discontinuation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169690A (en) * | 1994-10-21 | 1998-01-07 | 大金工业株式会社 | Release agent, hardened skin-film obtained from said release agent and forming method using said release agent |
| US6808379B2 (en) * | 2001-05-10 | 2004-10-26 | Samsung Electronics Co., Ltd. | Cleaner for molding apparatus of semiconductor chip packages |
| CN101060995A (en) * | 2004-11-24 | 2007-10-24 | 分子制模股份有限公司 | Method and composition providing desirable characteristics between a mold and a polymerizable composition |
| CN101795838A (en) * | 2007-09-06 | 2010-08-04 | 3M创新有限公司 | Form the method for mould and use described mould to form the method for goods |
| TW201100242A (en) * | 2009-06-19 | 2011-01-01 | Tokyo Electron Ltd | Imprint system, imprint method, program and computer recording medium |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012147728A1 (en) | 2012-11-01 |
| JPWO2012147728A1 (en) | 2014-07-28 |
| KR20140021644A (en) | 2014-02-20 |
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