CN106707375A - Optical film and preparation method thereof - Google Patents
Optical film and preparation method thereof Download PDFInfo
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- CN106707375A CN106707375A CN201611133618.0A CN201611133618A CN106707375A CN 106707375 A CN106707375 A CN 106707375A CN 201611133618 A CN201611133618 A CN 201611133618A CN 106707375 A CN106707375 A CN 106707375A
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- preparation
- refractive index
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
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Abstract
The invention relates to the field of a semiconductor and especially relates to an optical film and a preparation method thereof. The preparation method of the optical film comprises performing a film-plating process by use of a design membrane system of a mixed material comprising two materials and a third material, wherein the refractive index of the mixed material is greater than that of the third material. The refractive index of the prepared optical film is uniform, the performance of the film is good, and the performance of a photoetching object lens can be improved.
Description
Technical field
The present invention relates to semiconductor applications, more particularly to a kind of optical thin film and preparation method thereof.
Background technology
As the development of semi-conductor industry, the characteristic size of large scale integrated circuit are less and less, photoetching technique is used as system
The key technology of standby semiconductor devices, faces new challenges.In order to improve the resolution ratio of etching system, the wavelength of exposure light source
Constantly reduce, from 436nm, the near ultraviolet of 355nm enters into 248nm, the deep ultraviolet band of 193nm.With 193nm ArF quasi-molecules
As a example by laser lithography, 90nm, 65nm and 45nm nodes, the exposure technique as current main flow have been broken through.
In deep ultraviolet band lithographic objective, component size is generally all larger in optical system, and bending is compared on surface,
New requirement is proposed to coating process.In deep ultraviolet band, most Coating Materials have strong absorption, it is possible to use
Few, the only very few several fluorides and oxide of Coating Materials.Therefore, based on this limitation, it is difficult to obtain
Obtain the Coating Materials of specific refractive index.Meanwhile, when coated element compares bending than larger, surface, due to component size and plating
The reason for film coating materials evaporation incidence angle, available these Coating Materials can typically be presented more serious refractive index inhomogeneity, lead
Cause element optical property everywhere difference occur, bring the decline of image quality, have a strong impact on the performance of optical thin film, govern
The manufacture of lithographic objective.
The content of the invention
It is contemplated that overcoming deep ultraviolet band heavy caliber curved surface elements in the prior art, generally there is folding in the film being coated with
The inhomogeneities of rate is penetrated, causes element optical property everywhere difference occur, the problems such as bring the decline of image quality, there is provided one
Refractive index homogeneity is planted, the performance of film is good, can improve optical thin film of performance of lithographic objective and preparation method thereof.
To achieve the above object, the present invention uses following technical scheme：
The invention provides a kind of preparation method of optical thin film, including from containing two kinds of mixing materials and the 3rd of material
Design of material membrane system, carries out coating process；Wherein, the refractive index of mixing material is more than the 3rd material.
In some embodiments, the mixing material contains the first material and the second material, and the refractive index of first material is big
In the second material；The content of first material is more than the second material.
In some embodiments, on the basis of the weight percentage of the mixing material, the content of first material is
50%-90%.
In some embodiments, the second material is identical with the material of the 3rd material.
In some embodiments, the first material, the second material and the 3rd material the optical thin film service band according to obtained in enter
Row material selection；First material and the second material absorb small in obtained optical thin film service band.
In some embodiments, obtained optical thin film service band is deep ultraviolet band.
In some embodiments, first material is lanthanum fluoride or gadolinium fluoride；Second material and the 3rd material are each
It is independently magnesium fluoride or aluminum fluoride.
In some embodiments, design membrane system is to design membrane system using the refractive index of mixing material and the 3rd material.
In some embodiments, the refractive index of mixing material passes through step：S1, two kinds of materials in mixing material point
The ratio between subnumber extrapolates the refractive index coarse value of mixing material；S2, technological experiment is carried out to mixing material, and according to coarse value pair
The result of technological experiment is fitted, and obtains the refractive index exact value of mixing material.
The present invention additionally provides optical thin film prepared by above-mentioned preparation method simultaneously.
The beneficial effects of the present invention are：
The present inventor has to use for two kinds of different refractivities by long-term research discovery in coating process
Coating Materials in, be high-index material the reason for produce larger refractive index inhomogeneity, and it is high to select mixing material to replace
Refraction materials, monofilm technological experiment is carried out by mixing material；Go out the folding of mixing material by the ratio estimate for mixing
Rate coarse value is penetrated, then the result using the value for technological experiment is fitted, and obtains the exact value of mixing material refractive index,
After obtaining these parameters, then membrane system is designed with low-index material using mixing material, carry out coating process, efficiently solved
The larger problem of the film refractive index inhomogeneities of deep ultraviolet band heavy caliber curved surface elements, improves the performance of film, method letter
It is single easy to operate.
The present invention to equipment without carrying out upgrading；New Coating Materials need not be bought；The present invention is simple to operate, is familiar with
Coating process and technological parameter fitting etc. can be operated.
Brief description of the drawings
Fig. 1 is LaF3The curve of spectrum, a is LaF3Transmitted spectral curve, b is fused silica chip H103 resin.Wherein, a is every
In theory should be tangent with substrate transmittance curve at individual crest, if nontangential, prove that Coating Materials has refractive index uneven
Property.
Fig. 2 is LaF3Dispersion of refractive index curve, i.e., refractive index is with the curve of wavelength change.
Fig. 3 is MgF2The curve of spectrum, c is MgF2Transmitted spectral curve, d is fused silica chip H103 resin.Wherein, c is every
In theory should be tangent with substrate transmittance curve at individual trough, if nontangential, prove that Coating Materials has refractive index uneven
Property, deviation it is more, refractive index inhomogeneity is bigger.
Fig. 4 is MgF2Dispersion of refractive index curve, i.e., refractive index is with the curve of wavelength change.
Fig. 5 is the curve of spectrum of the mixing material of embodiment 1, and e is the transmitted spectral curve of mixing material, and f is fused quartz
Substrate H103 resin.As can be seen that refractive index inhomogeneity is compared with LaF3It is much smaller.
Fig. 6 is the dispersion of refractive index curve of the mixing material of embodiment 1.
Fig. 7 is two-sided deep ultraviolet antireflective film transmitance result test curve prepared by embodiment 1.
Specific embodiment
Embodiments of the invention are described below in detail, specific embodiments described below is exemplary, it is intended to for solving
The present invention is released, and is not considered as limiting the invention.
The invention provides a kind of preparation method of optical thin film, including from containing two kinds of mixing materials and the 3rd of material
Design of material membrane system, carries out coating process；Wherein, the refractive index of mixing material is more than the 3rd material.Using mixing material with it is low
Refraction materials design membrane system, carry out coating process, efficiently solve the film refraction of deep ultraviolet band heavy caliber curved surface elements
The larger problem of rate inhomogeneities, improves the performance of film, and method is simple to operation.
Mixing of the mixing material containing the first material and kind of the material of the second material, i.e., two, as long as in mixing material of the invention
Two kinds of materials can realize that physical arrangement is complementary, and the refractive index of the first material and the second material can be the same or different,
Selected as needed.Specifically, in some embodiments, the refractive index of the first material is more than the second material；Further preferably,
The content of first material is more than the second material, is conducive to being designed to high and low refractive index in design membrane system, i.e. some embodiments
The mixing material of material mixing, the refractive index of two kinds of materials of selection is different, and the content of preferably high-index material is big.And
And, the refractive index of the refractive index more than the 3rd material of mixing material.
Specifically, in some embodiments, on the basis of the weight percentage of mixing material, the content of the first material is
50%-90%.
In a particular embodiment of the present invention, the second material is identical with the 3rd material, i.e., a kind of material in mixing material
It is identical with the single material that follow-up coating process is used.
Typically, according to the service band of required optical thin film, suitable low-refraction Coating Materials high is chosen, specifically,
First material, the second material and the 3rd material the optical thin film service band according to obtained in carry out material selection；First material
Material and the second material absorb small in obtained optical thin film service band.
It is of the invention that preferably obtained optical thin film service band is deep ultraviolet band, method of the invention is particularly suitable for
The optical thin film of deep ultraviolet band is prepared, can effectively solve the problem that the film refractive index of deep ultraviolet band heavy caliber curved surface elements is uneven
The larger problem of even property, improves the performance of film, and without carrying out upgrading to equipment；New Coating Materials need not be bought；
The present invention is simple to operate, is operated by being familiar with coating process and technological parameter fitting etc..
Specifically, the present invention preferably the first material is lanthanum fluoride or gadolinium fluoride；Second material and the 3rd material are each
It is independently magnesium fluoride or aluminum fluoride, is to be capable of achieving the present invention by the low-refraction Coating Materials high commonly used.
In some embodiments, design membrane system designs membrane system using the refractive index of mixing material and the 3rd material.
Specifically, the refractive index of preferable blendstocks of the present invention passes through step：S1, two kinds of materials in mixing material
The ratio between molecular number extrapolate the refractive index coarse value of mixing material；S2, technological experiment is carried out to mixing material, and according to rough
Value is fitted to the result of technological experiment, obtains the refractive index exact value of mixing material, and follow-up coating process is determined using this
Refractive index design membrane system.
Specific step can be as follows:
(1) according to the service band of required optical thin film, suitable low-refraction Coating Materials high is chosen；
(2) they are mixed according to a certain percentage, wherein based on high-index material；
(3) according to the ratio of mixing, the refractive index coarse value of mixing material is extrapolated；
(4) technological experiment is carried out to mixing material, and the result of technological experiment is intended according to the coarse value for estimating
Close, obtain the accurate refractive index of mixing material；
(5) using parameters such as the mixing material refractive indexes and known low-index material for obtaining, membrane system is designed, is plated
Membrane process.
Wherein, design membrane system, coating process are known to the skilled person, and will not be repeated here.
The present invention additionally provides optical thin film prepared by above-mentioned preparation method simultaneously.Obtained optical film refractive index is equal
Even, the performance of film is good, can improve the performance of lithographic objective.
The following is the specific embodiment that the present invention is provided, it is used to the selection for illustrating such scheme and its various conditions.This hair
Agents useful for same is pure using analysis purchased in market in bright embodiment.
Embodiment 1
The present embodiment is used to illustrate the DUV film that preparation work wave band is 193nm.
(1) LaF is chosen3(lanthanum fluoride) and MgF2(magnesium fluoride) material；By the spectrum test curve map 1 of lanthanum fluoride, can be with
Obtain the lanthanum fluoride refractive index curve parameter such as Fig. 2；By the spectrum test curve map 3 of magnesium fluoride, the fluorine such as Fig. 4 can be obtained
Change magnesium refractive index curve parameter；
(2) by high-index material (LaF3) and low-index material material (MgF2) with mass ratio 9:1 is mixed and made into mixing
Material；
(3) according to LaF in mixing material3And MgF2Ratio (9:And LaF 1)3And MgF2Relative molecular mass (respectively
For 190 and 58) the ratio between their molecular number (namely the ratio between thin film composition) can be obtained, then in conjunction with LaF3And MgF2At 193nm
Refractive index value (respectively 1.712 and 1.429) extrapolate the refractive index coarse value of mixing material and be about 1.636；
(4) by the result of technological experiment, that is, can be obtained such as Fig. 6 as the mixing material curve of spectrum of Fig. 5 is fitted
Mixing material dispersion of refractive index curve；
(5) membrane system is designed by the refractive index of such as low-index material of the mixing material of Fig. 6 and Fig. 4, carries out plated film work
Skill.
Sample is tested using PerkinElmer1050 type spectrophotometers.Test condition：Set test-types as
T% patterns (transmission-type), it is 185-400nm, a width of 2nm of band of each light extraction of monochromator to set test wavelength scope, tests number
It is 1nm according to acquisition interval, is 0.6s per the nm times of integration.Specific steps：It is first empty in sample room after photometer is preheated 15 minutes
Autozero curves are scanned in the case of putting, as standard zero line.Then, sample is fixed on specimen holder, in test condition
Sample is scanned in the case of not changing, curve obtained is the transmittance curve of sample.It is dark purple to the present embodiment gained
Outer optical thin film carries out spectrum test and obtains transmitance result test curve as shown in Figure 7.It is of the invention dark purple as can be seen from Figure 7
Outer optical thin film refractive index homogeneity, good in optical property.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or spy that the embodiment or example are described
Point is contained at least one embodiment of the invention or example.In this manual, to the schematic representation of above-mentioned term not
Necessarily refer to identical embodiment or example.And, the specific features of description, structure, material or feature can be any
One or more embodiments or example in combine in an appropriate manner.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art is not departing from principle of the invention and objective
In the case of above-described embodiment can be changed within the scope of the invention, change, replace and modification.
Claims (10)
1. a kind of preparation method of optical thin film, it is characterised in that including from containing two kinds of mixing materials of material and the 3rd material
Material design membrane system, carries out coating process；The refractive index of the mixing material is more than the 3rd material.
2. preparation method according to claim 1, it is characterised in that the mixing material contains the first material and the second material
Material, the refractive index of first material is more than the second material, and the content of first material is more than the second material.
3. preparation method according to claim 2, it is characterised in that the weight percentage with the mixing material is as base
Standard, the content of first material is 50%-90%.
4. preparation method according to claim 2, it is characterised in that the material phase of second material and the 3rd material
Together.
5. preparation method according to claim 2, it is characterised in that the first material, the second material and the 3rd material according to
Obtained optical thin film service band carries out material selection；First material and the second material work in obtained optical thin film
Wave band absorbs small.
6. preparation method according to claim 5, it is characterised in that the obtained optical thin film service band is dark purple
Wave section.
7. preparation method according to claim 6, it is characterised in that first material is lanthanum fluoride or gadolinium fluoride；Institute
It is independently each magnesium fluoride or aluminum fluoride to state the second material and the 3rd material.
8. preparation method according to claim 1, it is characterised in that the design membrane system is using mixing material and the 3rd
The refractive index design membrane system of material.
9. preparation method according to claim 8, it is characterised in that the refractive index of the mixing material passes through step：S1、
The ratio between two kinds of molecular numbers of material in mixing material extrapolate the refractive index coarse value of mixing material；S2, to mixing material
Material carries out technological experiment, and the result of technological experiment is fitted according to coarse value, and the refractive index for obtaining mixing material is accurate
Value.
10. the optical thin film that prepared by a kind of preparation method as described in claim 1-9 any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611133618.0A CN106707375A (en) | 2016-12-10 | 2016-12-10 | Optical film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611133618.0A CN106707375A (en) | 2016-12-10 | 2016-12-10 | Optical film and preparation method thereof |
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| CN106707375A true CN106707375A (en) | 2017-05-24 |
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| CN201611133618.0A Pending CN106707375A (en) | 2016-12-10 | 2016-12-10 | Optical film and preparation method thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101925837A (en) * | 2007-11-30 | 2010-12-22 | 康宁股份有限公司 | Be used for dense homogeneous fluoride films of DUV element and preparation method thereof |
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2016
- 2016-12-10 CN CN201611133618.0A patent/CN106707375A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101925837A (en) * | 2007-11-30 | 2010-12-22 | 康宁股份有限公司 | Be used for dense homogeneous fluoride films of DUV element and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 唐晋发等: "《现代光学薄膜技术》", 30 November 2006 * |
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| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170524 |
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| RJ01 | Rejection of invention patent application after publication |