CN1126747A

CN1126747A - Multifunctional optical material and component written in by UV, visible light and X ray and read out by IR

Info

Publication number: CN1126747A
Application number: CN 95111736
Authority: CN
Inventors: 陈述春; 戴凤妹
Original assignee: Shanghai Institute of Optics and Fine Mechanics of CAS
Current assignee: Shanghai Institute of Optics and Fine Mechanics of CAS
Priority date: 1995-04-06
Filing date: 1995-08-25
Publication date: 1996-07-17
Anticipated expiration: 2015-08-25
Also published as: CN1049915C

Abstract

The said multifunctional optical material is synthesized with alkaline earth sulphide as matrix component, metal copper ion as main doping activator and samarium and cerium ions as supplementary activator, and it is made into multifunctional optical component through high-temp roasting. As multiple multilayer material and component, they are used for the storage, digital writing in and reading out of UV, visible light and X-ray picture and other information, anti-fake trade mark and invisible code.

Description

The UV, visible light X ray writes infrared multifunctional optical material of reading and element thereof

The present invention is the optical material and the element thereof of a kind of light or image storage, and this material can store ionizing rays such as ultraviolet and X-ray or image, and the image that will store under the infrared light effect shows with visible luminous form then; Perhaps, after this material is to ultraviolet photoetching, has the function that resembling of near-infrared radiation can be converted to visible light or image.Material of the present invention is also to the visible light sensitivity, thereby is a kind of multi-functional light or visual storage medium.

Material with similar functions mostly is the IIa-VIb compounds of group that is mixed with two kinds of rare earth ions, SrS (Eu for example, 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 efficient is lower, and material is not easy to do stablely [to see U.S. Pat 4806772 (HO5B33/00); US4812659 (HO5B33/00); US 4812660 (HO5B33/00)].Since have darker trap in these materials, trapped electron that can be stable, and just think just can cause photoluminescence that this phenomenon has been used to make the infrared sensor that near infrared light is responded with relevant material with near infrared light (λ＜1.7 μ m).The image storage and the conversion element that also are used for simultaneously optical storage and information processing.

Main purpose of the present invention provides a kind of UV, visible light and X-ray image storage medium and element, the time of maintenance one fixed length that the image of this storage can be stable, and can be visual after with infrared excitation with visible luminous demonstrations.Be again a kind of infrared sensor or the infrared conversion element that resembles simultaneously, as long as it (after λ＜350nm) energy is filled in exposure, just can show infrared light or convert the imaging of infrared light on element to visible to resemble to ultraviolet.

Multifunctional optical material of the present invention is made of multi-element compounds.Its matrix components is an alkaline earth sulfide, and main component is special impurity, the characteristics of luminescence of its decision material, and other additive (alkaline-earth sulfate, alkali halide, alkali-earth halide etc.).Main matrix composition alkaline earth sulfide before not adding other composition, does not possess any available characteristic.Mix into that dominant activator is that metal copper ion makes its characteristic that has obtained photoluminescence, and mixing of second kind of promptly auxilliary activator samarium of impurity, cerium etc. makes it to have had optical storage and the infrared characteristic that goes up conversion.

The Chemical Composition of multifunctional optical material of the present invention:

Main component is an alkaline earth sulfide, wherein is mixed with two or more foreign ions, and a kind of is copper, and another kind is samarium and cerium, adds an amount of fusing assistant (as with alkaline-earth sulfate and alkaline earth fluoride, or with alkali fluoride etc.) simultaneously, increases luminous intensity.Rare earth ion can be an oxide compound, or sulfide or vitriol or the adding of halid form.Its relative weight ratio is:

SrS (83.66～99.94)·(1-x) wt％

CaS (83.66～99.94) x wt% is x=0～1 wherein

CuSO ₄ 0.05～0.20 wt％

Sm ₂O ₃ 0.01～0.06 wt％

Ce ₂O ₃ 0～0.08 wt％

LiF 0～8 wt％

CaF

₂ 0～4 wt％

CaSO

₄ 0～8 wt％

Use multifunctional optical material of the present invention and prepare infrared sensing element

1. above-claimed cpd is weighed up mixing in required ratio, be pressed into sheet after the grinding, put into High Temperature Furnaces Heating Apparatus afterwards, under inert atmosphere, heat, burnt 0.5-2.5 hour, promptly get optical material of the present invention after the cooling in 1000-1200 ℃ 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 and resin) after levigate, apply on transparent thin board substrate (as glass, quartz, synthetic glass sheet etc.), obtain the image processing element.

2. above-claimed cpd is weighed up in required ratio, directly be deposited on behind the mixed grinding on the resistant to elevated temperatures transparent substrate such as aluminum oxide, be placed on afterwards in the High Temperature Furnaces Heating Apparatus, under inert atmosphere, heat, burnt 0.5-2.5 hour in 1000-1200 ℃ of temperature, promptly get element of the present invention after the cooling.The above-mentioned element that makes can be coated with suitable protective membrane so that use according to different needs.

The main use of element of the present invention

1. the storage of ultraviolet X-ray image or optical information and processing.

2. binary data coding ,～350nm and～270nm writes, near infrared (λ=0.75-1.4 μ m) is read;

3. image or information processing;

4. anti-false trademark or stealthy sign indicating number;

5. multiplexed memory spare;

6. multilayer memory device.

Advantage of the present invention

1. characteristics such as it is fast to have the electron capture material response, differentiates height, and linearity range is big;

2. has dual write diagnostics.For example some element can write with～430nm, and also the light of available 350nm writes, and can show the information of not sharing the same light and writing simultaneously when near infrared light is read;

3. write optical wavelength～350 μ m and existing some electron capture material [as: SrS (Eu, Sm), SrS (Ce, Sm), CaS (En, Sm) and CaS (Ce, Sm) etc.] difference, the optical memory element of the multi-layer film structure that one-tenth multi-wavelength capable of being combined writes;

4. wavelength of transmitted light can be adjusted in the visible range of broad;

5. have multiple function and low cost of manufacture.

Description of drawings:

Fig. 1. luminescent spectrum distribution plan (ordinate is luminous intensity I, and abscissa is emission wavelength λ).

Fig. 2. infrared exiting spectrum response (ordinate is luminous intensity I, and abscissa is incentive optical wavelength λ).

Six, embodiment:

Example 1:

Press and form the synthetic a kind of material of branch, wherein each composition accounts for the total weight percent rate and is: (x=0)

SrS 90 wt％

CuSO ₄ 0.14 wt％

Sm ₂O ₃ 0.03 wt％

CaSO ₄ 6.23 wt％

CaF ₂ 3.6 wt％

Take by weighing strontium sulfide 9876mg, calcium sulfate 683.6mg, Calcium Fluoride (Fluorspan) 395.4mg, copper sulfate 15mg, Samarium trioxide 3.3mg according to the above ratio and mix and be placed in the electric furnace after grinding well, under 1000 ℃ of temperature, burnt 2.5 hours logical simultaneously argon gas.Must material of the present invention after the cooling, and then pulverize and sneak in transparent adhesive tape or the organic binder bond (as polymer, resin etc.) after levigate, on transparent substrate, make rete and promptly obtain element of the present invention.Its luminescent spectrum such as Fig. 1 curve 3.Infrared exiting spectrum is shown in Fig. 2 curve 1.

Example 2:

Press and composition with become a kind of material, wherein each compound accounts for total weight percent and is: (x=0.4)

SrS 68.8 wt％

CaS 27.5 wt％

CuSO ₄ 0.14 wt％

Sm ₂O ₃ 0.04 wt％

Ce ₂O ₃ 0.03 wt％

LiF 3.49 wt％

Taking by weighing strontium sulfide 22786mg, sulfurated lime 9107.78mg, copper sulfate 46.35mg and Samarium trioxide 13.2mg, cerium oxide 10mg, Lithium Oxide 98min 1155.86mg according to the above ratio mixes and is placed in the alumina crucible after grinding well, in electric furnace, under 1150 ℃ of temperature, burnt 1.0 hours logical simultaneously argon gas.Can get material of the present invention and element thereof after the cooling.Its luminescent spectrum is shown in Fig. 1 curve 4.Infrared exiting spectrum such as Fig. 2 curve 2.

Example 3:

Press and composition is made a kind of material, wherein each compound accounts for total weight percent and is:

(x＝0)

SrS 90.84 wt％

CuSO ₄ 0.05 wt％

Sm ₂O ₃ 0.01 wt％

CaSO

₄ 5 wt％

LiF 4.1 wt％

Taking by weighing strontium sulfide 51866mg, calcium sulfate 2854.8mg, lithium fluoride 2340.9mg, copper sulfate 28.56mg and Samarium trioxide 5.8mg according to aforementioned proportion mixes and is placed in the alumina crucible after grinding well, in the electric furnace internal heating, under 1020 ℃ of temperature, burnt 2 hours logical simultaneously argon gas.After the cooling the various methods of filming of the levigate usefulness of gained material are made film and promptly obtain element of the present invention.Its luminescent spectrum is shown in Fig. 1 curve 2.Infrared exiting spectrum such as Fig. 2 curve 1 show.

Example 4:

Make a kind of material by following composition, wherein each compound accounts for total weight percent and is: (x=0)

SrS 90.8 wt％

CuSO ₄ 0.10 wt％

Sm ₂o ₃ 0.04 wt％

Ce ₂O ₃ 0.06 wt％

LiF 9 wt％

Taking by weighing strontium sulfide 17498mg, copper sulfate 19.27mg and Samarium trioxide 7.7mg, cerium oxide 11.5mg, Lithium Oxide 98min 1734.38mg according to aforementioned proportion mixes and is placed in the alumina crucible after grinding well, in the High Temperature Furnaces Heating Apparatus internal heating, under 1050 ℃ of temperature, burnt 1.5 hours logical simultaneously argon gas.Get final product after the cooling material of the present invention and element.Its excitation luminescence spectrum is shown in Fig. 1 curve 5.Infrared exiting spectrum is shown in Fig. 2 curve 1.

Example 5:

Press and composition is made another material, wherein the weight percent of the relative CaS of each compound is: (x=1)

CaS 83.88 wt％

CuSO ₄ 0.10 wt％

Sm ₂o ₃ 0.02 wt％

LiF 8 wt％

CaSO ₄ 8 wt％

Taking by weighing sulfurated lime 20554.7mg, copper sulfate 24.5mg and Samarium trioxide 4.9mg, calcium sulfate 1960.39mg, lithium fluoride 1960.39mg according to aforementioned proportion mixes and is placed in the alumina crucible after grinding well, in the High Temperature Furnaces Heating Apparatus internal heating, under 1200 ℃ of temperature, burnt 0.5 hour logical simultaneously argon gas.After the cooling the various sides of filming of the levigate usefulness of gained material are sent out and make film and be element of the present invention, its excitation luminescence spectrum is shown in Fig. 1 curve 1.Infrared exiting spectrum is shown in Fig. 2 curve 3.

Claims

1. a UV, visible light X ray writes the infrared multifunctional optical material of reading, matrix components is an alkaline earth sulfide, be doped with samarium, cerium ion, add an amount of alkaline-earth sulfate, alkali fluoride and alkaline earth fluoride as fusing assistant, it is characterized in that adulterated dominant activator is a metal copper ion, auxilliary activator is samarium, cerium ion, and its Chemical Composition relative weight ratio is:

SrS (83.66～99.94)·(1-x) wt％

CaS (83.66～99.94) x wt% is x=0～1 wherein

CuSO ₄ 0.05～0.20 wt％

Sm ₂O ₃ 0.01～0.06 wt％

Ce ₂O ₃ 0～0.08 wt％

LiF 0～8 wt％

CaF ₂ 0～4 wt％

CaSO ₄ 0～8 wt％

Weigh up each compound according to the above ratio, be pressed into sheet behind the mixed grinding, put into High Temperature Furnaces Heating Apparatus, under inert atmosphere, heat, under 1000～1200 ℃ temperature, fired 0.5～2.5 hour, promptly get material of the present invention after the cooling.

2. a UV, visible light X ray writes the infrared multifunctional optical element of reading, and is that the employing matrix components is an alkaline earth sulfide, doping dominant activator cupric ion, and the multifunctional optical material of auxilliary activator samarium, cerium ion, the concrete Chemical Composition of material is:

SrS (83.66～99.94)·(1-x)?wt％

CaS (83.66～99.94) x wt% is x=0～1 wherein

CuSO ₄ 0.05～0.20 wt％

Sm ₂O ₃ 0.01～0.06 wt％

Ce ₂O ₃ 0～0.08 wt％

LiF 0～8 wt％

CaF ₂ 0～4 wt％

CaSO ₄ 0～8 wt％

The starting material that prepare according to the above ratio behind mixed grinding, are deposited on the resistant to elevated temperatures substrate, put into High Temperature Furnaces Heating Apparatus, are heated in 1000～1200 ℃ the temperature to fire 0.5～2.5 hour the multifunctional optical element that the cooling back is obtained under inert atmosphere.