CN1034277A - hologram - Google Patents
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- CN1034277A CN1034277A CN 88100539 CN88100539A CN1034277A CN 1034277 A CN1034277 A CN 1034277A CN 88100539 CN88100539 CN 88100539 CN 88100539 A CN88100539 A CN 88100539A CN 1034277 A CN1034277 A CN 1034277A
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- microclearance
- phase hologram
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Abstract
The invention discloses volume phase hologram and other holographic element, it comprises that a kind of refractive index is different from the micro-district of the material of hologram fringe refractive index.
Description
The present invention relates to volume phase hologram and other holographic element, be the preparation of volume phase hologram He other holographic element of feature with the micro-district with material especially, and this material has the refractive index different with the refractive index of hologram fringe.This new holographic element can present diffraction efficiency and/or other the desirable performance that increases.
Volume phase hologram also is the hologram that refractive index is modulated, and is that everybody knows, and has been prepared by various photochromicss, and especially those are by photopolymerization or the crosslinked hologram that forms hologram fringe.
Double color cement (DCG) has been widely used for making volume phase hologram.Though proposed multiple mechanism, the mechanism that forms hologram image in DCG also do not understood fully.A kind of suggestion is to form " crack " or " space " between the fringe plane of glue, and this causes the difference between (in crack or the space) refractive index of air and the refractive index of glue, and causes the raising of index modulation.(see A.Graube, " Holographic optical element materials research ", U.S.Air Force Office of Scientifio Research Technical Report78-1626(1978), can particularly obtain in the 95-113 page or leaf wherein from the DTIC Technical Report ADAD 62692 of U.S.Defense Technical Information Center.) at one piece of paper (R.K.Curran and T.A.Shankoff early, " The mechanism of Hologram Formation in Dichromated Gelatin ", Applied optics, July, 1970, V.9, the 1651-1657 page or leaf, especially see 1655 pages) in the appearance in " space " has been proposed dispute, the conclusion of this article is the interphase that " space " caused air-gelatin ".(B.J.Chang in another piece publication in 1980, " Dichromated Gelatin Holograms and their Applications; Optical Engineering; V; 19; P642-648 sees P642-643 especially) a kind of mechanism also proposed: " strand elasticity " model.Also having another kind of mechanism is to interact between propyl alcohol and the gelatin, when eliminating isopropyl alcohol, crack, this be by J.R.Magarinos and D.J.Coleman propose can be referring to " Holographic Mirrors ", Optical Engineering, 1985, V.24, P769-780.These researchers recognize to keep and present slit (micro chink) and be the method for prerequisite, can incur loss owing to the method for replacing the air in the slit with a kind of fluid with the refractive index that is complementary with gelatin makes holographic efficient, but whether can draw a kind of like this conclusion as for them, be discrepant on degree.Obviously, the just mechanism that these researchers studied, rather than the method for improvement optical property.
Be disclosed in 4 of the U.S. on May 13rd, 1986 by Herbert L.Fielding and Richard T.Ingwall, 586, in No. 644 patents, a kind of composition that forms the useful especially photopolymerization of volume phase hologram is described and has proposed claim.These photopolymerization potpourris comprise a kind of dye sensitiser, and methylene blue for example is as branch's polyethyleneimine of polymerization initiator and a kind of polymerising ethylene unsaturation monomer of free radical, preferably acrylic monomers and acrylic acid lithium.A kind ofly form the method for stable hologram, make an explanation in the United States Patent (USP) 4,535,041 disclosed and propose claim on August 13rd, 1985 by Herbert L.Fielding and Richard T.Ingwall by the photosensitive polymerization potpourri.
By the present invention, propose between striped, to have a kind of refractive index and hologram fringe to reflect volume phase hologram and other holographic element of the microscopic region of the different material of number.
Below the present invention is explained in detail.As well-known in holographic technique and understanding, volume phase hologram has write down the information as the medium refraction index modulation, and record is a final purpose here.Therefore, appear at tranquil wooden Feng of light daughter-in-law Feng ∧ ぶ tool ヌ offer cooked food magnesium figure spade agent custom Chi Feng hold in the mouth an ancient spear scar lift up beer by a word used in person's names pacify anti-and Fu of muddled towering barium raise The turn sour ⑵ give birth Suan U rooms at the sides of or facing the principal rooms ┨ lift up tired straightforward words spouse bridle ring porcelain Guan dumpling ⒄ palm Xing edge narrow cry the bright dried Guan dumpling ⒄ palm snail of the quiet of apricot joke straightforward words spouse bridle the strange joke river which rises in the northeastern part of Anhui Province of sheltering of edge ancient wine vessel: the punishment is lifted up frequently wooden Feng's rank and is carved and wash the outspoken straightforward words of the bright of the sweet of Qian wash with watercolours to lift up that Pu wet herds be the sweet of the angry Qian wash with watercolours badger Jia Lun Chi fashionable tired paddy ⑾ benefit attendant of the bride or bridegroom at a wedding frame of sweet land measure of 30 mu at dusk tomb badger that covers
At above-mentioned U.S.4, point out in 588,664, by to do the micro-scanning electron microscope check surface of light with the micromechanism of the formed hologram of photopolymerization synthetic material, between the photopolymer striped, present the microclearance that comprises air; The transversal section of these microclearances is normally spherical.Though, the appearance that they separate in electron microscope, these microclearances are interconnected.The alternate planes of solid and porous (being connected the microclearance) material is presented on by in separately each of bragg condition layer.The 50-80% that typically has a diameter from distance between adjacent solid phase place (striped) of these microclearances, for example: the holographic reflected light components of may serving as reasons approximately half of catoptrical wavelength.Air is contained in these microclearances, and their density changes with exposure intensity.It is believed that, the appearance of these microclearances, the monomer in the rete is to the result that the regional transverse dispersion of polymerization takes place at least.
Remove water and other solvent through photopolymerisable rete development and drying for monomer, thereby air is charged into, formed the microclearance.Because there is the ability of certain scattered light the microclearance of filling air, so this holographic element may present to a certain degree the optical haze relevant with the size of microclearance.
Having now found that, with another kind of material repeatedly and reversibly, or is permanently to replace part of air in the gap at least, and the mutual spacing that changes hologram fringe significantly is possible, and this additional material is preferably for good and all stayed holographic element inside.Adopt this method, can make light characteristic/holographic performance produce desirable variation, because a small amount of variation of refractive index between photopolymerisable (striped) zone and the additional materials or optical density has enlarged the influence to this system optics characteristic.For simplicity, the material of replacing air in the microclearance can be called " microclearance material ".
The material of replacing air in the microclearance is to import holographic element by the solution that infiltrates this kind material or this material, promptly is the method that adopts dipping.This additional materials may be a kind of material that can further react, and as a kind of polymerisable monomer or a kind of crosslinked compound, to be incorporated in the holographic element be effective and so further reaction is for for good and all oozing said material.Oozing of polymerisable monomer closed and can be acted on simultaneously with the polymerizable initiating agent, perhaps is better to import initiating agent earlier, then imports polymerisable monomer again.The selection of initiating agent and monomer should avoid producing or forming any undesirable dyeing.For obtaining in the microclearance than low refractive index polymers, preferably useful monomer is through fluoridizing especially fluoridized monomer.Can produce polymerization by any known method, for example ultraviolet is brought out monomer or the analog that is used to holographic matrix material.In some cases; a kind of film that produces polymkeric substance also can be formed on the surface of hologram; and a kind of like this film of polymkeric substance can provide the protection on the additional physical property, and is for example moistureproof or prevent that other from influencing the environmental factor of hologram stability or optical property.In addition, also can utilize so a kind of surface aggregate thing film that hologram is adhered on another kind of material or the hologram.
The microclearance material can be a kind of dyestuff or other light-absorbing compound.Therefore, can the light of predetermined wavelength or wave band be absorbed.This device is for providing the holographic notch light filter, and for example for eyes provide protection, it is particularly useful to make it to avoid the laser hazard aspect, because final formed optical density (transmitance) will be reflector laser and the synthesis result that absorbs laser.Owing to suitably select additional absorber of light, people can improve the optical density of relevant wavelength in the basic transmitance of keeping other wavelength simultaneously; therefore can strengthen protection to the user; and make visual aspects, promptly visible light cause undesirable, or undue loss.Because the difference of the refractive index between additional materials and " striped " polymkeric substance is littler than the difference between striped and air, made it to reduce the optical haze degree of holographic element.In some cases, this also may cause the decline of diffraction efficiency, if particularly this hologram is a kind of reflection-type.But the benefit that reduces optical haze may be than the benefit that remedies diffraction efficiency decline for big.In fact, if this additional materials is at certain spectral region, be similar to the refractive index that the refraction with the striped polymkeric substance is complementary as in the visible range, having, and in another zone, infrared region for example, their refractive index difference when then obtaining the strong reflection rate in other zone, can be eliminated the optical haze in the first area basically.
Filling can then be finished with respect to the perviousness of test material to determine hologram by conventional test by selecting to close the material that accords with the refractive index that requires in the selection of the suitable material of microclearance.People will recognize that suitable microclearance material may be different with both composition variations with the combination of hologram matrix material.Usually, it is suitable adopting the refractive index of its refractive index and hologram matrix to differ 0.1 microclearance material at least, and the index difference is big more, and the influence that is obtained is just big more.Because it is suitable having selected the microclearance material that matrix is expanded or expand minimum for use, the index difference heals the big influence that obtains just more greatly.Owing to select the microclearance material and the solvent that do not make matrix expand or expand minimum for use, the spacing between the striped can be remained unchanged basically; Otherwise if selected microclearance material and the solvent that matrix is expanded for use, the interval of then having write down between the plane of striped may increase.
Because the mean refractive index of microclearance filling film is than the refractive index height of the microclearance of filling with air, so the wavelength of the maximum reflectivity of reflection holography photo shifts to the long wave end, i.e. red end, and be accompanied by the decline of diffraction efficiency.This performance can be used for regulating the wavelength of maximum reflectivity in the arrowband holographic filter.Along with the difference of filling the selected material refractive index in microclearance, the adjusting that peak wavelength is predicted on about 50-100nm scope is possible.
In transmission-type hologram situation, owing to the existence of microclearance material is offset the peak value angle of diffraction.Because the efficient of this grating periodically changes with grating intensity (it becomes with exposure), the microclearance material may improve, and also may reduce grating diffration efficient.
If the microclearance material has optical activity, promptly it presents different refractive indexes for dextrorotation and left circularly polarized light, makes hologram that the light of two kinds of polarizations is presented different performances like this.For example, if in fact the microclearance material in a kind of reflection holography photo has identical refractive index for a kind of polarization state of light as matrix, then the circularly polarized light of this kind form will be reflected consumingly.The infiltration type hologram of a kind of like this microclearance of adding material will make the circularly polarized light of two kinds of forms be diffracted into different angles.
People will recognize, the size of infiltrating material in the microclearance should be enough little, so that can enter in the microclearance fully, and this size will become with the size of microclearance.
Can select the microclearance material to improve the environmental stability of hologram,, or reduce or eliminate and couple together the harmful effect that is caused with bonding agent or plastifier for example to the stability of humidity and/or temperature.(it is to do to handle continuously and α-cyanoethyl acrylic acid glue at above-mentioned U.S3, is not adopted in not filling microclearance yet in 588,664 the example 3 with zirconates and fatty acid that the stability of describing in above-mentioned U.S 4,535,041 is handled).
Therefore for convenience's sake, adopted US 4,588,664 and the disclosure of US 4,535,041.Following example is for illustrative purposes, and is not to mean to make restriction.
Example 1
Adopt the photopolymer film of form described in above-mentioned U.S 4,588,664 examples 7 to prepare the hologram of infiltration type, carry out general exposure and stabilized treatment by the described light of described example (633nm) then with he-Ne laser.At last, the film thickness of treated drying (not including matrix) approximately is 6 microns.With visible spectrophotometer the hologram of doing is done to see through spectral analysis, show the spectral width of about 170nm, and 83% maximum diffraction efficiency is arranged at the 565nm place.When TFE (refractive index 1.29) was infiltrated in the dry type hologram, spectral bandwidth reduced about 60nm, and maximum diffraction efficiency is increased to 87% slightly, and the wavelength shift of maximal efficiency is to about 635nm place.TFE goes out hologram with isopropyl alcohol and acetone rinsing respectively, and makes the hologram drying, allows hologram infiltrate general electric silicone oil SF99(refractive index 1.39 then); Measure diffraction efficiency and be about 58%, the wavelength of maximal efficiency is 630nm.
Example 2
On transmission hologram photo, put a spot of 1% solution that is dissolved in the diphenylhydroxyethanone ethylether in the dimethylbenzene, and allow dimethylbenzene evaporate by 1 described method preparation, then with the two acrylic acids of a spot of PFPE:
H
2C＝CH-CO
2-CH
2CF
2O（CF
2O）
X（CF
2CF
2O）
X
CF
2CH
2 =CH
2(molecular weight about 2100; Refractive index 1.31) drops on the holographic plate, it is spread on the hologram image scope, cover with a glass then, the hologram that has soaked into monomer exposed 10 minutes down at ultraviolet light (405nm), then exposed 10 minutes under the ultraviolet light of 365nm, after the UV exposure first time, can see that the cover-plate glass sheet is fixed and go up in position, discovery after the UV exposure second time, with initial stage 74% efficiency ratio, its diffraction efficiency approximately is 20%.Cover-plate glass is removed, and hologram is put into water boiled about one and a half hours, find that afterwards efficient reaches about 22%.With hologram from its glass pedestal shift out form one deck complete but a bit fragile no tread support membrane.
Example 3
Make and be dissolved in CF
2(CF
2)
6CH
2 =CH
2In the diethoxy third ethyl ketone solution and example 2 in used fluoridized monomer mixture infiltrated, by the method energy density of example 1 be 15 millijoules/centimetre
2The prepared transmission hologram photo of helium-neon laser exposure in.Then, this hologram is with ultraviolet lighting 15 minutes, the diffraction efficiency that can find the hologram handled like this and initial 22% compare and can reach 70%.
Example 4
Step in the example 2 repeatedly is used for presenting when the 490nm diffraction efficiency greater than 99% reflection holography photo, and through uv-exposure 20 minutes.Found that, in the microclearance, include diffraction efficiency, when 585nm, reach 80%, after about 15 hours of 150 ℃ of heating, find that the diffraction efficiency of the reflection holography photo handled is 87% at 540nm through the hologram of the perfluorinated polymers of aggregation processing.
Example 5
To make with example 1 described conventional method with helium-neon laser, the holographic mirror (reflection holography photo) at the photopolymerization layer center on a glass basis is coated with the iodeosin solution that last layer is dissolved in TFE.After the solvent evaporation, photopolymerization layer pinkiness.Such dyeing can not be used isopropyl acetone, and the water mixed liquid that contains of methyl alcohol or these alcohol rinses out.The holographic mirror of this dyeing is carried out optical density (transmission) spectrophotometry of some incident angles, and the result shows that this dyes holographic Jing Qu when incident angle 0-40 spends, and has one greater than 5 peak light density on 530 and 555 wavelength.By comparing, holographic mirror original when vertical incidence has 2.8 peak light density at the 580nm place, and there is one 3.5 peak light density in the non-holographic district of dyeing at the 540nm place.Original holographic mirror just remains visible to reflected light.Measure based on these, can draw iodeosin at least in part filling the conclusion of microclearance.
Self-evident, other can prepare the polymkeric substance of volume phase hologram and the corresponding place that bonding agent can be applied to employed those materials in the above-mentioned example, and the suitable microclearance material that is provided can be impregnated in the hologram.
Clearly, hologram of the present invention can adopt suitable bonding, for example optics epoxy adhesive and being integrated with other optical devices.In addition, these holograms can be by whole sealing, or only its edge is carried out sealing to increase its stability to environment.
As long as, and, obviously just can make various variations, and not depart from spirit of the present invention and scope to those the skilled artisan in the art with reference to embodiment according to detailed description of the present invention.
Claims (14)
1, a kind of body phase hologram element is characterized in that microclearance other the outer material of filling deacration at least in part between the striped, and said material has the refractive index different with the matrix refractive index.
2, a kind of by the body phase hologram element that claim 1 limited, it is characterized in that described refractive index is lower than the refractive index of matrix.
3, a kind of by the body phase hologram element that claim 1 limited, it is characterized in that described matrix comprise branch's polyethyleneimine and a kind of polymerization vinyl monomer.
4, a kind of as the volume phase hologram that claim 3 limited, it is characterized in that described monomer is a kind of acrylic acid.
5, a kind of as the body phase hologram element that claim 1 limited, it is characterized in that described material is a hydrophobe.
6, a kind of as the volume phase hologram that claim 1 limited, it is characterized in that described material with low refractive index is a kind of fluorinated monomer of polymerization.
7, a kind of as the body phase hologram element that claim 6 limited, the thin layer that it is characterized in that said polymerization fluorinated monomer is to be presented on the surface of described holographic element.
8, one for as the volume phase hologram that claim 1 limited, and it is characterized in that described material is a kind of material that can absorb by certain wavelength light of described holographic element reflection.
9, the method that forms a kind of holographic element comprises with laser light activated element is made holographic exposure, described light activated element through exposure is carried out photographic fixing, preparing a kind of body phase hologram element that the microclearance is arranged between striped, and with a kind of material that differing refraction indices arranged described microclearance of filling at least in part.
10,, it is characterized in that described light activated element is a kind of photopolymerizable element by the method that claim 9 limited.
11,, it is characterized in that described photopolymerizable element comprises a kind of dyeing sensitizer, branch's polyethyleneimine, and the polymerizable ethylene unsaturated monomers of a kind of free atom group by the method that claim 9 limited.
12, by the method that claim 9 limited, the tool feature is to comprise a kind of polymerisable monomer is infiltrated described microclearance, makes described monomer polymerization then, has the step of the material of low-refraction with preparation.
13,, it is characterized in that described monomer is the monomer that a kind of process is fluoridized by the method that claim 12 limited.
14,, it is characterized in that described monomer through fluoridizing is aggregated in the lip-deep step of described holographic element with becoming skim by the method that claim 13 limited.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100539 CN1023035C (en) | 1988-01-08 | 1988-01-08 | Holograms |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100539 CN1023035C (en) | 1988-01-08 | 1988-01-08 | Holograms |
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| Publication Number | Publication Date |
|---|---|
| CN1034277A true CN1034277A (en) | 1989-07-26 |
| CN1023035C CN1023035C (en) | 1993-12-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88100539 Expired - Fee Related CN1023035C (en) | 1988-01-08 | 1988-01-08 | Holograms |
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| Country | Link |
|---|---|
| CN (1) | CN1023035C (en) |
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1988
- 1988-01-08 CN CN 88100539 patent/CN1023035C/en not_active Expired - Fee Related
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| CN1023035C (en) | 1993-12-08 |
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