CN1059304C - High-efficient optical recording and upper conversion material and element thereof - Google Patents
High-efficient optical recording and upper conversion material and element thereof Download PDFInfo
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- CN1059304C CN1059304C CN95111735A CN95111735A CN1059304C CN 1059304 C CN1059304 C CN 1059304C CN 95111735 A CN95111735 A CN 95111735A CN 95111735 A CN95111735 A CN 95111735A CN 1059304 C CN1059304 C CN 1059304C
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Abstract
The present invention relates to high efficiency material for optical record and up-conversion and an element thereof. The material can absorb and store ultraviolet light and visual light and can release the stored energy in a visual light form under the action of infrared light. The present invention provides material and an element thereof, wherein the material simultaneously comprises two substrate constituents of SrS and CaS and poly-alkali soil sulfide simultaneously mixed with impurity ions of europium, samarium and cerium. The present invention has the advantages of wide application range, high response speed, high luminous efficiency, wide range of response and output spectra, etc.
Description
The present invention a kind ofly has the material of optical storage and upper conversion function and adopts the prepared element of this material.This material can absorption and store ultraviolet and visible light, and under the infrared light effect energy of the storage form with visible light is discharged; The information of being carried by ultraviolet or optical photon (or image) can be stored or be write down to this in other words material and the orange-red light signal sense information to show under the near infrared light effect.On the other hand, after this material is to visible (blue green) light or ultraviolet photoetching, has the function that information translation that infrared photon nearly carries becomes visible (orange red) light.
Material with similar functions mostly is the IIa-VIb compounds of group that is mixed with two kinds of rare earth ions, and people just find that this compounds has the characteristic of Infrared Stimulated Luminescence before 40 years, and is called infrared excitation phosphor.But because preparation is difficult, efficient is low, does not obtain development and utilization all the time.Up in recent years, along with the development of laser and photonic propulsion, wherein some is suggested, as the infrared-sensitive material that near infrared light is responded with as the functional material in optical storage and the information processing is developed.Since have darker trap in these materials, trapped electron that can be stable, and just think just can cause luminescence generated by light that thermal effect is minimum with near infrared light (λ ∠ 1.6 μ m).And luminescence process has very little time constant, particularly output intensity and input (write or read) light intensity has the bigger range of linearity, it all is the advantage of this material, the material such as the SrS (Eu of patent have been applied, Sm), good photoluminescence property is arranged, it can write and launch orange light with blue light, SrS (Ce and for example, Sm) can export green glow, but they all are the materials of only mixing two kinds of impurity and single-matrix, and efficient is lower, and material is not easy to do stablely [to see U.S. Pat 48 06772 (HO5B33/00); US 4812659 (HO5B33/00); US 4812660 (HO5B33/00)].
Main purpose of the present invention provides a kind of high efficiency ultraviolet and visible light storage medium and element, and the maintenance considerable time that the image of this storage can be stable is when with the luminous displayed image of energy after infrared ray excited.
That is to say that with the made element of this material be a kind of infrared sensor or the infrared conversion element that resembles, as long as it (after λ＜300nm) and visible (460-560nm) light exposure fill energy, just can convert orange-red light and image to infrared light or with resembling of becoming of infrared light with the highest efficient to ultraviolet on element.
Material of the present invention is for containing two kinds of host material SrS and CaS simultaneously, and is mixed with the polynary alkaline earth sulfide of three kinds of impurity (europium, samarium and cerium etc.) simultaneously.Wherein divalent europium has fabulous photoluminescence property.Cerium ion both can have been done dominant activator adjustment output light color also can play auxilliary activator with samarium ion.This material has wideer luminescent spectrum coverage, higher efficient and longer infrared response wavelength.Under the allotment of special process conditions and other chemical composition, suitable charge compensation mechanism can guarantee that europium ion and the part cerium ion in the material forms efficient luminescence center, and samarium ion and part cerium ion form electron trap, under ultraviolet and blue green glow effect, the electron excitation of luminescence center is to conduction band or highly excited level, and electrons excited is transferred in the electron trap by conduction band or interionic excitation state tunnel process.Because trap is quite dark, very stable by its duplet heat of capturing, so just being stored in trap with the form of trapped electron density, the energy that excites suffered.Have only when encouraging with near infrared light, electronics just overflow trap outer with the hole-recombination of staying on the luminescence center.This photoelectron motion process and mechanism provide unique optical storage and upper conversion function for this material.And have and can wipe, can rewrite, speed is fast, the efficient height, threshold energy is low, and the range of linearity is big, low cost and other advantages.
The chemical analysis of material of the present invention is:
Main component is polynary alkaline earth sulfide, contains two kinds of matrix components: SrS and CaS, wherein is mixed with three kinds of foreign ions simultaneously, and a kind of is europium, other be samarium and cerium, simultaneously add an amount of alkaline-earth sulfate again, alkaline earth fluorides etc. are as flux.Rare earth ion can be an oxide, or sulfide or the adding of halid form.Its relative raw material total weight percent is:
SrS (83.8～99.96)·(1-x)?wt％
CaS (83.8～99.96) x wt% is x=0.05～0.95 wherein
CaSO
4 0～10 wt％
CaF
2 0～6 wt％
Eu
2O
3?0.020～0.08 wt％
Sm
2O
3?0.010～0.06 wt％
Ce
2O
3?0.005～0.06 wt％
Above-claimed cpd is weighed up mixing in required ratio, be placed on after the grinding in the resistant to elevated temperatures alumina crucible, be placed on afterwards in the high temperature furnace, under inert atmosphere, heat, burnt 0.5-3 hour, promptly get material of the present invention after the cooling in 1000-1250 ℃ of temperature.With the above-mentioned material block that makes, pulverize and sneak in transparent adhesive tape or certain the organic bonding agent (as polymer or resin) after levigate, directly make the polymer film.Or apply on thin transparent substrate (as glass, quartz, polymethyl methacrylate sheet etc.), as image processing and light conversion element.Or apply on opaque substrate (as paper, fiber board, the various adhesive sticker scraps of paper etc.), be used for infrared acquisition and sensing element.
Above-claimed cpd is weighed up in required ratio, adopt film build method to be deposited on the resistant to elevated temperatures transparent substrates such as aluminium oxide behind the mixed grinding, be placed on afterwards in the high temperature furnace, under inert atmosphere, heat, burnt 0.5-3 hour in 1000-1250 ℃ of temperature, promptly get element of the present invention after the cooling.
The advantage of material of the present invention and prepared element is:
1. purposes is wide, can be used as
(1) ultraviolet or visible light information stores;
(2) infrared going up changed or surveyed;
(4) anti-false trademark or stealthy sign indicating number;
(5) multiplexed memory spare;
(6) multilayer memory device.
2. be characterized in having and can wipe, can rewrite, speed is fast, and particularly the present invention is for mixing the polynary alkaline earth sulfide of three kinds of impurity simultaneously, and than the alkaline earth sulfide luminous efficiency height of mixing two kinds of impurity in the prior art, threshold energy is low, and the big and cost of the range of linearity is low etc.;
3. the output light wavelength scope is big, can write the color that light inlet is adjusted read output signal with different;
4. infrared response spectrum can arrive 1.6 μ m, is applicable to the light conversion of infrared optical fiber, and higher sensitivity is arranged;
Description of drawings:
Fig. 1. visible light writes spectral distribution (ordinate is that luminous intensity is got arbitrary unit, and abscissa is for writing wavelength).
Fig. 2. infrared response spectral distribution (ordinate is that luminous intensity is got arbitrary unit, and abscissa is for reading wavelength).
Fig. 3. Infrared Stimulated Luminescence spectral distribution graph (ordinate is that luminous intensity is got arbitrary unit, and abscissa is an emission wavelength).
Embodiment:
Embodiment 1:
By the synthetic a kind of material of following composition, the percentage that each composition accounts for the raw material total weight is:
SrS 87.93 wt％(x＝0.05)
CaS 4.6 wt％
CaSO
4 4.63 wt％
CaF
2 2.77 wt％
Eu
2O
3 0.04 wt％
Sm
2O
3 0.025 wt％
Ce
2O
3 0.005 wt％
Taking by weighing the raw material that strontium sulfide 21742mg, calcium sulfide 1138mg, calcium sulfate 1144.86mg, calcirm-fluoride 684.94mg, europium oxide 9.89mg, samarium oxide 6.18mg, cerium oxide 1.24mg mix after grinding well according to the above ratio is placed in the alumina crucible, under 1000 ℃ of temperature, in high temperature furnace, burnt 2.5 hours logical simultaneously argon gas.Can get material of the present invention after the cooling, its visible light energy storage spectrum such as Fig. 1 are shown in the curve 1.Infrared exiting spectrum such as Fig. 2 are shown in the curve 1.And excitation luminescence spectrum such as Fig. 3, shown in the curve 1.
Fine powder is worn in the block pulverizing of sintering, sneaked in the adhesive (as polymer, resin etc.), apply on various thin slab substrate (papery, fiber, glass, quartz, aluminium flake, polymethyl methacrylate etc.), can do infrared sensor behind the plastic packaging.Or directly make polymer (as polymethyl methacrylate) film, do picture inversion and record usefulness.
Embodiment 2:
By the synthetic a kind of material of following composition, the percentage that each composition accounts for the raw material total weight is:
SrS 70.12 wt％(x＝0.2)
CaS 17.53 wt％
CaSO
4 7.88 wt％
CaF
2 4.38 wt％
Eu
2O
3 0.02 wt％
Sm
2O
3 0.01 wt％
Ce
2O
3 0.06 wt％
Taking by weighing the raw material that strontium sulfide 18866mg, calcium sulfide 4716.5mg, calcium sulfate 2120.14mg, calcirm-fluoride 1178.45mg, europium oxide 5.38mg, samarium oxide 2.69mg, cerium oxide 16.14mg mix after grinding well according to the above ratio is placed in the alumina crucible, under 1100 ℃ of temperature, in high temperature furnace, burnt 0.5 hour logical simultaneously argon gas.Can get material of the present invention after the cooling, its visible light energy storage spectrum such as Fig. 1 are shown in the curve 2.Infrared exiting spectrum such as Fig. 2 are shown in the curve 2.And excitation luminescence spectrum such as Fig. 3, shown in the curve 2.
Embodiment 3:
By the synthetic a kind of material of following composition, the percentage that each composition accounts for the raw material total weight is:
SrS 41.97 wt％(x＝0.5)
CaS 41.97 wt％
CaSO
4 10 wt％
CaF
2 5.94 wt％
Eu
2O
3 0.06 wt％
Sm
2O
3 0.04 wt％
Ce
2O
3 0.02 wt％
Taking by weighing the raw material that strontium sulfide 30946.6mg, calcium sulfide 30946.6mg, calcium sulfate 7373.5mg, calcirm-fluoride 4379.86mg, europium oxide 44.24mg, samarium oxide 29.49mg, cerium oxide 14.75mg mix after grinding well according to the above ratio is placed in the alumina crucible, in electric furnace, under 1050 ℃ of temperature, burnt 1.5 hours logical simultaneously argon gas.Can get material of the present invention after the cooling, its visible light wave range energy storage spectrum such as Fig. 1 are shown in the curve 3.Infrared exiting spectrum response is as Fig. 2, shown in the curve 3.Excitation luminescence spectrum such as Fig. 3 are shown in the curve 3.
Fine powder is worn in the block pulverizing of sintering, sneaked in the adhesive (as polymer, resin etc.), apply on various thin slab substrate (papery, fiber, glass, quartz, aluminium flake, polymethyl methacrylate etc.), can do infrared sensor behind the plastic packaging.Or directly make polymer (as polymethyl methacrylate) film, do picture inversion and record usefulness.
Embodiment 4:
By the synthetic a kind of material of following composition, the percentage that each composition accounts for raw material weight is:
By the synthetic a kind of material of following composition, the percentage that each composition accounts for raw material weight is:
SrS 4.99 wt％(x＝0.95)
CaS 94.86 wt％
Eu
2O
3 0.08 wt％
Sm
2O
3 0.06 wt％
Ce
2O
3 0.005 wt％
Taking by weighing the raw material that strontium sulfide 2394.5mg, calcium sulfide 45521.5mg, europium oxide 38.39mg, samarium oxide 28.79mg, cerium oxide 2.4mg mix after grinding well according to the above ratio is deposited on the optical flat of high temperature resistant crystal with any film build method, in high temperature furnace, under 1250 ℃ of temperature, burnt 3 hours logical simultaneously argon gas.Can get element of the present invention after the cooling.Its visible light writes spectrum such as Fig. 1, shown in the curve 4.Infrared exiting spectrum such as Fig. 2 are shown in the curve 4.And corresponding excitation luminescence spectrum such as Fig. 3, shown in the curve 4.
Claims (2)
1. high efficiency optical recording and up-conversion, main component is an alkaline earth sulfide, form with compound is doped with foreign ion europium, samarium and cerium, add an amount of alkaline-earth sulfate and alkaline earth fluoride again as flux, it is characterized in that polynary alkaline earth sulfide of the present invention contains two kinds of host material: SrS and CaS simultaneously, and be doped with three kinds of foreign ions simultaneously: europium, samarium and cerium, concrete chemical analysis are (by weight percentage):
SrS (83.8～99.96)·(1-x) wt％
CaS (83.8～99.96) x wt%_ is x=0.05～0.95 wherein
CaSO
4 0～10 wt％
CaF
2 0～6 wt％
Eu
2O
3 0.020～0.08 wt％
Sm
2O
3 0.010～0.06 wt％
Ce
2O
3 0.005～0.06 wt％
Behind mixed grinding, put into high-temperature crucible by the raw material of above-mentioned formula rate, in high temperature furnace, under inert atmosphere, calorify under 1000～1250 ℃ the temperature and burn to 0.5～3 hour, the cooling back obtains material of the present invention.
2. a high efficiency optical recording and last conversion element, used material main component is an alkaline earth sulfide, be doped with foreign ion europium, samarium and cerium, it is characterized in that the material that is adopted is to contain SrS and two kinds of matrix compositions of CaS simultaneously, and the polynary alkaline earth sulfide of while europium doped, samarium and three kinds of foreign ions of cerium, when the proportioning material, be to mix into above-mentioned three kinds of foreign ion europiums, samarium and ceriums with the form of compound, concrete content (by weight percentage) is:
SrS (83.8～99.96)·(1-x) wt％
CaS (83.8～99.96) x wt% is x=0.05～0.95 wherein
CaSO
4 0～10 wt％
CaF
2 0～6 wt％
Eu
2O
3 0.020～0.08 wt％
Sm
2O
3 0.010～0.06 wt％
Ce
2O
3 0.005～0.06 wt％
By the raw material that above-mentioned content ratio weighed up, behind mixed grinding, adopt film build method to be deposited on the resistant to elevated temperatures transparent substrates, put into high temperature furnace, the temperature that calorifies 1000 ℃～1250 ℃ under inert atmosphere was fired 0.5～3 hour, cooling back gained element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111735A CN1059304C (en) | 1995-08-25 | 1995-08-25 | High-efficient optical recording and upper conversion material and element thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111735A CN1059304C (en) | 1995-08-25 | 1995-08-25 | High-efficient optical recording and upper conversion material and element thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1124910A CN1124910A (en) | 1996-06-19 |
| CN1059304C true CN1059304C (en) | 2000-12-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95111735A Expired - Fee Related CN1059304C (en) | 1995-08-25 | 1995-08-25 | High-efficient optical recording and upper conversion material and element thereof |
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|---|---|
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925154B (en) * | 2012-11-23 | 2014-04-16 | 中国科学院长春光学精密机械与物理研究所 | Sulfide-based triple-doped electron trapping material and preparation method thereof |
| CN103435351A (en) * | 2013-08-01 | 2013-12-11 | 长春理工大学 | Up-conversion luminescent sulfide ceramic |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4806772A (en) * | 1985-10-10 | 1989-02-21 | Quantex Corporation | Infrared sensing device outputting orange light and a process for making the same |
| US4812660A (en) * | 1985-10-10 | 1989-03-14 | Quantex Corporation | Photoluminescent materials for outputting yellow-green light |
| US4812659A (en) * | 1985-10-10 | 1989-03-14 | Quantex Corporation | Infrared sensing device outputting blue-green light |
-
1995
- 1995-08-25 CN CN95111735A patent/CN1059304C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4806772A (en) * | 1985-10-10 | 1989-02-21 | Quantex Corporation | Infrared sensing device outputting orange light and a process for making the same |
| US4812660A (en) * | 1985-10-10 | 1989-03-14 | Quantex Corporation | Photoluminescent materials for outputting yellow-green light |
| US4812659A (en) * | 1985-10-10 | 1989-03-14 | Quantex Corporation | Infrared sensing device outputting blue-green light |
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| Publication number | Publication date |
|---|---|
| CN1124910A (en) | 1996-06-19 |
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