CN110028966A - A kind of orthosilicate base deep ultraviolet long after glow luminous material and preparation method thereof - Google Patents

A kind of orthosilicate base deep ultraviolet long after glow luminous material and preparation method thereof Download PDF

Info

Publication number
CN110028966A
CN110028966A CN201910403086.5A CN201910403086A CN110028966A CN 110028966 A CN110028966 A CN 110028966A CN 201910403086 A CN201910403086 A CN 201910403086A CN 110028966 A CN110028966 A CN 110028966A
Authority
CN
China
Prior art keywords
deg
deep ultraviolet
luminous material
glow luminous
ln
Prior art date
Application number
CN201910403086.5A
Other languages
Chinese (zh)
Inventor
梁延杰
毕见强
孙康宁
王伟礼
Original Assignee
山东大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 山东大学 filed Critical 山东大学
Priority to CN201910403086.5A priority Critical patent/CN110028966A/en
Publication of CN110028966A publication Critical patent/CN110028966A/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7774Aluminates; Silicates

Abstract

Present disclose provides a kind of orthosilicate base deep ultraviolet long after glow luminous material and preparation method thereof, including matrix, active ions and co-dopant ions, the matrix is Ln2SiO5, one of Ln Lu, Y, Gd or two kinds, active ions Pr3+, co-dopant ions Li+、Na+Or K+One of.The material of the disclosure can produce deep ultraviolet light transmitting when high energy light excites.After light source is removed, which still is able to generate lasting deep-UV light-emitting, and the long-persistence luminous peak value of deep ultraviolet is located at 280nm and 320nm two, and persistence is greater than 1h.The deep ultraviolet long after glow luminous material day blind ultraviolet imagery, disinfection and sterilization, photocatalysis, the fields such as anti-fake and medical optical dynamic therapy have potential application value.

Description

A kind of orthosilicate base deep ultraviolet long after glow luminous material and preparation method thereof

Technical field

The disclosure belongs to long after glow luminous material technical field, is related to a kind of long-persistence luminous material of orthosilicate base deep ultraviolet Material and preparation method thereof.

Background technique

Here statement only provides background information related with the disclosure, without necessarily constituting the prior art.

Long-persistence luminous to refer to the phenomenon that material still is able to continuous illumination after external world's excitation stops, extraneous excitaton source can To be ultraviolet light, sigmatron, sunlight etc., the duration that shines is from several seconds to several weeks etc..It is sent out with this long afterglow The material of optical property is referred to as long after glow luminous material.In recent years, it is contemplated that ultraviolet long after glow luminous material is in photocatalysis, disinfection The potential using value in the fields such as sterilization, ultraviolet imagery, anti-fake and optical dynamic therapy, new ultra-violet long after glow luminous material are opened Hair and research are just gradually causing the concern of domestic and foreign scholars.But compared to visible light and near-infrared long after glow luminous material research institute The series progress of acquirement, twilight sunset emission band are located at the long after glow luminous material of ultraviolet region (200~400nm), especially have The deep ultraviolet long after glow luminous material that twilight sunset launch wavelength is less than 320nm is closed, according to known to the disclosed invention people, due to by matrix The limitation of material and the centre of luminescence, current research and application are relatively fewer, and progress is also relatively slow.Although reported several Ultraviolet long after glow luminous material, such as CdSiO3:Bi3+、Sr2MgGe2O7:Pb2+Deng, can ultraviolet region generate long afterglow transmitting. But by the disclosed invention people the study found that the twilight sunset launch wavelength range of these materials and persistence all manage not enough Think that (its main emitting area is located at the long wave ultraviolet light area (UVA) of 320~400nm, and part light emitting region is still in visible light Area), and the heavy metal ion (Cd contained in material2+And Pb2+Deng) reality that can also limit them to a certain extent answers With.For this reason, it may be necessary to develop the novel deep ultraviolet long after glow luminous material with shorter launch wavelength and longer persistence.

Summary of the invention

In order to solve the deficiencies in the prior art, purpose of this disclosure is to provide a kind of orthosilicate base deep ultraviolet long afterglow hairs The twilight sunset emission peak of luminescent material and preparation method thereof, the afterglow materials is located at 280nm and 320nm two, persistence Greater than 1h.

To achieve the goals above, the technical solution of the disclosure are as follows:

On the one hand, a kind of orthosilicate base deep ultraviolet long after glow luminous material, including matrix, active ions and codope from Son, the matrix are Ln2SiO5, one of Ln Lu, Y, Gd or two kinds, active ions Pr3+, co-dopant ions Li+、Na+Or K+One of.

On the other hand, a kind of preparation method of above-mentioned orthosilicate base deep ultraviolet long after glow luminous material, with Ln salt, praseodymium salt With alkali metal salt as raw material, presoma xerogel is obtained by sol-gal process using citric acid and ethyl orthosilicate, will before It drives soma gel to be calcined, obtains orthosilicate base deep ultraviolet long after glow luminous material, the Ln salt includes Lu3+、Y3+、Gd3+ One of or two kinds, the alkali metal salt include Li+、Na+Or K+One of.

The third aspect, a kind of above-mentioned orthosilicate base deep ultraviolet long after glow luminous material day blind ultraviolet imagery, photocatalysis, It is disinfection and sterilization, anti-fake and/or prepare application in medical optical dynamic therapy reagent.

The disclosure has the beneficial effect that

(1) the deep ultraviolet long after glow luminous material of disclosure design and exploitation function admirable needs suitable deep-UV light-emitting Center and matrix, they will determine respectively deep ultraviolet long after glow luminous material launch wavelength and ultraviolet persistence.This public affairs The active ions Pr that choice-start is selected3+High efficiency and broad band deep ultraviolet can be generated by 4f5d → 4f energy level transition in rare earth orthosilicate Light emitting.In addition, the disclosure, using rare earth orthosilicate as matrix, internal lattice defect can be used as trap level, In excitation process storage energy and excitation stop after transferring energy to Pr3+

(2) material of disclosure preparation shows the long-persistence luminous performance of strong deep ultraviolet.Ultraviolet twilight sunset emission peak position At 280nm and 320nm two, persistence is greater than 1h.The deep ultraviolet long after glow luminous material day blind ultraviolet imagery, light urges There is potential application value in the fields such as change, disinfection and sterilization, anti-fake and medical optical dynamic therapy.

(3) preparation method that the disclosure uses, raw material drawing is extensive, cheap, easy to operate, does not need atmosphere Protection is suitble to large-scale industrial production.

Detailed description of the invention

The Figure of description for constituting a part of this disclosure is used to provide further understanding of the disclosure, and the disclosure is shown Meaning property embodiment and its explanation do not constitute the improper restriction to the disclosure for explaining the disclosure.

Fig. 1 is the X ray diffracting spectrum of deep ultraviolet long after glow luminous material prepared by the embodiment of the present disclosure 1;

Fig. 2 is the excitation spectrum and emission spectrum of deep ultraviolet long after glow luminous material prepared by the embodiment of the present disclosure 1;

Fig. 3 is the deep ultraviolet long after glow luminous material of the preparation of the embodiment of the present disclosure 1 through 254nm ultraviolet light irradiation 15 minutes, The long afterglow attenuation curve measured after light source is removed, upper right side illustration is the deep ultraviolet that material measures after irradiation stops 30 minutes Long afterglow emission spectrum.

Specific embodiment

It is noted that described further below be all exemplary, it is intended to provide further instruction to the disclosure.Unless another It indicates, all technical and scientific terms used herein has usual with disclosure person of an ordinary skill in the technical field The identical meanings of understanding.

It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root According to the illustrative embodiments of the disclosure.As used herein, unless the context clearly indicates otherwise, otherwise singular Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.

In view of the deficiencies of existing ultraviolet long after glow luminous material emitting area is undesirable, persistence is shorter, in order to solve Technical problem as above, the present disclosure proposes a kind of orthosilicate base deep ultraviolet long after glow luminous material and preparation method thereof.

A kind of exemplary embodiment of the disclosure provides a kind of orthosilicate base deep ultraviolet long after glow luminous material, packet Matrix, active ions and co-dopant ions are included, the matrix is Ln2SiO5, one of Ln Lu, Y, Gd or two kinds, activation Ion is Pr3+, co-dopant ions Li+、Na+Or K+One of.

Pr3+4f2Electron configuration is easy to 4f2An electron excitation to 5d energy level formed 4f15d1Configuration, when this The level of energy of 4f5d excited configuration exists1S0Under high excitation level, and and 4f2Spacing is nearest in configuration3P2Level spacing When sufficiently large, Pr3+The transmitting of high efficiency and broad band deep ultraviolet light can be generated by 4f5d → 4f energy level transition.Meanwhile the positive silicic acid of rare earth Salt is easy to produce lattice defect (such as Lacking oxygen, impurity defect) in high temperature preparation process, and the disclosure can using these defects With material internal formed trap level, and can in excitation process storage energy, promote Pr3+4f5d → 4f can be passed through Energy level transition generates the transmitting of high efficiency and broad band deep ultraviolet light, to obtain, twilight sunset launch wavelength is shorter and persistence is longer remaining Brightness luminescent material.

In one or more embodiments of the embodiment, Pr3+Doping concentration be 0.1%mol~5%mol.Work as Pr3+ Doping concentration be 0.5%mol~1%mol when, luminescent properties are more preferable.

In one or more embodiments of the embodiment, the doping concentration of co-dopant ions is 0%mol~5%mol, And the doping concentration of co-dopant ions is not 0.

The another embodiment of the disclosure provides a kind of above-mentioned orthosilicate base deep ultraviolet long after glow luminous material Preparation method is obtained using citric acid and ethyl orthosilicate by sol-gal process using Ln salt, praseodymium salt and alkali metal salt as raw material Presoma xerogel is obtained, presoma xerogel is calcined, obtains orthosilicate base deep ultraviolet long after glow luminous material, it is described Ln salt includes Lu3+、Y3+、Gd3+One of or two kinds, the alkali metal salt include Li+、Na+Or K+One of.

In one or more embodiments of the embodiment, Ln3+、Pr3+Integral molar quantity and citric acid molar ratio be 1: 1~3.Work as Ln3+、Pr3+Integral molar quantity and citric acid molar ratio be 1:2 when, the performance of afterglow materials is more preferable.

In one or more embodiments of the embodiment, the calcination process be first heating not higher than 900 DEG C (such as 700~900 DEG C) pre-burning is carried out, it then heats to not less than 1100 DEG C (such as 1100~1300 DEG C) and is sintered.Pre-burning can be with The volatile components in raw material are effectively removed, thus the ceramic powder that the sintering activity obtained is high, ingredient is uniform and stable.Therefore, exist In high-temperature sintering process, it is possible to reduce the shrinking percentage of material and the luminescent properties for effectively improving material.

In the series embodiment, tabletting is carried out after pre-burning, is then sintered.It can make the densification of powder body material after tabletting Degree greatly increases, and the crystal boundary facilitated between powder granule is mobile and crystal grain is grown up, therefore sintering temperature can be effectively reduced, and mentions The crystal property and luminescent properties of high material.

It in the series embodiment, is first ground after pre-burning, then carries out tabletting, be then sintered.

In the series embodiment, calcined temperature is 700~900 DEG C, and burn-in time is 1~3h.When calcined temperature be 790~ 810 DEG C, when burn-in time is 1.9~2.1h, the performance of afterglow materials is more preferable.

In the series embodiment, sintering temperature is 1100~1300 DEG C, and sintering time is 4~8h.When sintering temperature is 1245~1255 DEG C, when sintering time is 5.9~6.1h, the performance of afterglow materials is more preferable.

In one or more embodiments of the embodiment, calcining carries out in air atmosphere.Reducing atmosphere is not needed Protection.

In one or more embodiments of the embodiment, step are as follows:

(1) Ln salt, praseodymium salt and alkali metal salt are dissolved and obtains salting liquid;

(2) citric acid is added into salting liquid and is uniformly mixed acquisition mixed liquor;

(3) ethyl orthosilicate is added into mixed liquor, heating reaction obtains precursor sol;

(4) continue heating to precursor sol to be dried, obtain presoma xerogel;

(5) presoma xerogel is sintered, obtains orthosilicate base deep ultraviolet long after glow luminous material.

In order to preferably dissolve Ln salt, praseodymium salt, in the series embodiment, the solution of step (1) is the mixed of ethyl alcohol and water Close solution.When the volume ratio of ethyl alcohol and water is 3.9~4.1, the effect of dissolution Ln salt, praseodymium salt and alkali metal salt is more preferable.

In order to accelerate the dissolution of salt, in the series embodiment, the temperature dissolved in step (1) is 65~75 DEG C.

In order to preferably obtain afterglow materials, the salt in the disclosure uses nitrate, such as Ln salt is lutecium nitrate, nitre One or both of sour yttrium or gadolinium nitrate, praseodymium salt praseodymium nitrate.

In the series embodiment, the temperature dissolved in step (2) is 65~75 DEG C.

In the series embodiment, the reaction temperature of step (3) is 65~75 DEG C, and the reaction time is 4~6h.

In the series embodiment, step (4) drying temperature is 95~105 DEG C, and drying time is 12~16h.

In the series embodiment, the process of step (5) are as follows: pre-burning is carried out in low temperature oven after the grinding of presoma xerogel, Powder after pre-burning is put into high temperature furnace, is sintered and cooled in air atmosphere after regrinding and tabletting.

Embodiment there is provided a kind of above-mentioned orthosilicate base deep ultraviolet long after glow luminous material to exist for the third of the disclosure It is day blind ultraviolet imagery, photocatalysis, disinfection and sterilization, anti-fake and/or prepare application in medical optical dynamic therapy reagent.

In order to enable those skilled in the art can clearly understand the technical solution of the disclosure, below with reference to tool The technical solution of the disclosure is described in detail in the embodiment of body.

Embodiment 1

By 2.339gLu (NO3)3·6H2O, 0.0054g Pr (NO3)3·6H2O, 0.0043g NaNO3Be added to 40mL without In water-ethanol and the mixed solution of 10mL deionized water, and the stirring and dissolving under 70 DEG C of water-baths.It states in mixed solution then up 2.101g citric acid is added, continuation is stirred under 70 DEG C of water-baths.It is added after citric acid is completely dissolved, then into mixed solution The ethyl orthosilicate of 0.557mL continues stirring 4 hours until forming vitreosol, colloidal sol is then transferred to vacuum oven In 100 DEG C drying 12 hours.Obtained presoma xerogel is polished, the pre-burning 2h at 800 DEG C.Powder after pre-burning passes through After re-grinding, it is about 15mm, the disk that thickness is about 1mm that the powder of 1g or so, which is pressed into diameter, using powder compressing machine.Most Afterwards, by disk after molding, high temperature sintering 6h obtains Lu at 1250 DEG C2SiO5: 0.5%Pr3+, 2%Na+Deep ultraviolet long afterglow hair Luminescent material.

Sample is prepared to embodiment to detect:

The X-ray diffractogram of sample is referring to Fig. 1, with Lu2SiO5Standard diffraction spectrum (JCPDS 41-0239) it is consistent.Fig. 1 The sample for illustrating synthesis is pure monoclinic phase Lu2SiO5, no other miscellaneous phases generation.

Referring to fig. 2, under the excitation of 254nm high energy UV, sample can produce the excitation spectrum and emission spectrum of sample Strong deep-UV light-emitting, emission peak are located at 280nm and 320nm two.The wave-length coverage of excitation spectrum is arrived positioned at 200nm Between 275nm.

The deep ultraviolet long afterglow attenuation curve of sample excites 15min through 254nm high energy UV, removes referring to Fig. 3, sample After light source, it is long-persistence luminous to can produce deep ultraviolet, and persistence is greater than 1 hour.The twilight sunset launch wavelength of monitoring is 280nm. Upper right side illustration is the twilight sunset emission spectrum that sample measures after excitation stops 30 minutes in Fig. 3, is sent out with the luminescence generated by light in Fig. 2 The spectral line shape for penetrating spectrum is consistent.

Embodiment 2

By 2.339g Lu (NO3)3·6H2O, 0.0109g Pr (NO3)3·6H2O, 0.0035g LiNO3It is added to 40mL In dehydrated alcohol and the mixed solution of 10mL deionized water, and the stirring and dissolving under 70 DEG C of water-baths.Mixed solution is stated then up Middle addition 2.101g citric acid, continuation are stirred under 70 DEG C of water-baths.It is added after citric acid is completely dissolved, then into mixed solution The ethyl orthosilicate of 0.557mL continues stirring 4 hours until forming vitreosol, colloidal sol is then transferred to vacuum oven In 100 DEG C drying 12 hours.Obtained presoma xerogel is polished, the pre-burning 2h at 800 DEG C.Powder after pre-burning passes through After re-grinding, it is about 15mm, the disk that thickness is about 1mm that the powder of 1g or so, which is pressed into diameter, using powder compressing machine.Most Afterwards, by disk after molding, high temperature sintering 6h obtains Lu at 1250 DEG C2SiO5: 1%Pr3+, 2%Li+Deep ultraviolet is long-persistence luminous Material.

Embodiment 3

By 2.339g Lu (NO3)3·6H2O, 0.0109g Pr (NO3)3·6H2O, 0.0050g KNO3Be added to 40mL without In water-ethanol and the mixed solution of 10mL deionized water, and the stirring and dissolving under 70 DEG C of water-baths.It states in mixed solution then up 2.101g citric acid is added, continuation is stirred under 70 DEG C of water-baths.It is added after citric acid is completely dissolved, then into mixed solution The ethyl orthosilicate of 0.557mL continues stirring 4 hours until forming vitreosol, colloidal sol is then transferred to vacuum oven In 100 DEG C drying 12 hours.Obtained presoma xerogel is polished, the pre-burning 2h at 800 DEG C.Powder after pre-burning passes through After re-grinding, it is about 15mm, the disk that thickness is about 1mm that the powder of 1g or so, which is pressed into diameter, using powder compressing machine.Most Afterwards, by disk after molding, high temperature sintering 6h obtains Lu at 1250 DEG C2SiO5: 1%Pr3+, 2%K+Deep ultraviolet is long-persistence luminous Material.

Embodiment 4

By 1.91g Y (NO3)3·6H2O, 0.0109g Pr (NO3)3·6H2O, 0.0069g LiNO3Be added to 40mL without In water-ethanol and the mixed solution of 10mL deionized water, and the stirring and dissolving under 70 DEG C of water-baths.It states in mixed solution then up 2.101g citric acid is added, continuation is stirred under 70 DEG C of water-baths.It is added after citric acid is completely dissolved, then into mixed solution The ethyl orthosilicate of 0.557mL continues stirring 5 hours until forming vitreosol, colloidal sol is then transferred to vacuum oven In 100 DEG C drying 12 hours.Obtained presoma xerogel is polished, the pre-burning 2h at 800 DEG C.Powder after pre-burning passes through After re-grinding, it is about 15mm, the disk that thickness is about 1mm that the powder of 1g or so, which is pressed into diameter, using powder compressing machine.Most Afterwards, by disk after molding, high temperature sintering 6h obtains Y at 1200 DEG C2SiO5: 1%Pr3+, 4%Li+Deep ultraviolet is long-persistence luminous Material.

Embodiment 5

By 1.167g Lu (NO3)3·6H2O, 0.9575g Y (NO3)3·6H2O, 0.0054g Pr (NO3)3·6H2O, 0.0064gNaNO3It is added in 40mL dehydrated alcohol and the mixed solution of 10mL deionized water, and stirs under 70 DEG C of water-baths molten Solution.Addition 2.101g citric acid in mixed solution is stated then up, and continuation is stirred under 70 DEG C of water-baths.It is completely dissolved to citric acid Afterwards, then into mixed solution the ethyl orthosilicate of 0.557mL is added, continues stirring 4 hours until forming vitreosol, then will Colloidal sol is transferred to 100 DEG C drying 12 hours in vacuum oven.Obtained xerogel is polished, the pre-burning 2h at 800 DEG C.In advance Powder after burning is after re-grinding, and it is about 15mm that the powder of 1g or so, which is pressed into diameter, using powder compressing machine, and thickness is about For the disk of 1mm.Finally, high temperature sintering 6h obtains LuYSiO at 1250 DEG C by disk after molding5: 0.5%Pr3+, 3%Na+Deep ultraviolet long after glow luminous material.

Embodiment 6

By 1.167g Lu (NO3)3·6H2O, 1.1275g Gd (NO3)3·6H2O, 0.0109g Pr (NO3)3·6H2O, 0.0043gNaNO3It is added in 40mL dehydrated alcohol and the mixed solution of 10mL deionized water, and stirs under 70 DEG C of water-baths molten Solution.Addition 2.101g citric acid in mixed solution is stated then up, and continuation is stirred under 70 DEG C of water-baths.It is completely dissolved to citric acid Afterwards, then into mixed solution the ethyl orthosilicate of 0.557mL is added, continues stirring 4 hours until forming vitreosol, then will Colloidal sol is transferred to 100 DEG C drying 12 hours in vacuum oven.Obtained xerogel is polished, the pre-burning 2h at 800 DEG C.In advance Powder after burning is after re-grinding, and it is about 15mm that the powder of 1g or so, which is pressed into diameter, using powder compressing machine, and thickness is about For the disk of 1mm.Finally, high temperature sintering 6h obtains LuGdSiO at 1250 DEG C by disk after molding5: 1%Pr3+, 2%Na+ Deep ultraviolet long after glow luminous material.

The luminescent properties of embodiment 2~6 are similar to the luminescent properties of embodiment 1.

Embodiment 7

The present embodiment is same as Example 1, the difference is that: it is not added with NaNO3

The afterglow materials of preparation can produce deep-UV light-emitting under 254nm ultraviolet excitation, and emission peak distinguishes position At 280nm and 320nm two, but under the conditions of same test, the photoluminescence intensity of sample can only achieve material in embodiment 1 1/3 or so.Sample excites 15min through 254nm high energy UV, and after removing light source, the deep ultraviolet afterglow time is very short, can only Continue a few minutes.This is because alkali metal ion can play the role of fluxing agent, the crystallinity of sample is improved.Meanwhile radius Lesser alkali metal ion is able to enter host material lattice, so that host material is generated distortion of lattice, to increase host material The defects of concentration.

Embodiment 8

The present embodiment is same as Example 1, the difference is that: Pr (NO3)3·6H2The additive amount of O is 0.0005g.

The afterglow materials of preparation can produce deep-UV light-emitting under 254nm ultraviolet excitation, and emission peak distinguishes position At 280nm and 320nm two.But under the conditions of same test, the photoluminescence intensity of sample obviously subtracts compared to material in embodiment 1 It is weak, and after removing 254nm ultraviolet source, the deep ultraviolet persistence of sample shortens.This is because the centre of luminescence in sample Lazy weight cause the long-persistence luminous performance of the deep ultraviolet of sample bad.

Embodiment 9

The present embodiment is same as Example 1, the difference is that: Pr (NO3)3·6H2The additive amount of O is 0.109g.

The afterglow materials of preparation can produce deep-UV light-emitting under 254nm ultraviolet excitation, and emission peak distinguishes position At 280nm and 320nm two.But under the conditions of same test, the photoluminescence intensity of sample sharply subtracts compared to material in embodiment 1 It is weak, and after removing 254nm ultraviolet source, the deep ultraviolet of sample is long-persistence luminous very faint, the ultraviolet afterglow time It can only continue tens seconds.This is because the quantity of the centre of luminescence excessively generates concentration quenching effect in sample, so as to cause sample The long-persistence luminous performance of the deep ultraviolet of product is bad.

Embodiment 10

The present embodiment is same as Example 1, the difference is that: obtained presoma xerogel is polished, and 1250 DEG C Lower high temperature sintering 6h.

The outer afterglow intensity of the initial violet of the afterglow materials of preparation and ultraviolet persistence will be weaker than embodiment 1 In sample.

Embodiment 11

The present embodiment is same as Example 1, the difference is that: obtained presoma xerogel is polished, at 800 DEG C Lower pre-burning 2h.Powder after pre-burning is after re-grinding, the high temperature sintering 6h at 1250 DEG C.

The outer afterglow intensity of the initial violet of the afterglow materials of preparation and ultraviolet persistence will slightly be weaker than implementation Sample in example 1.

The foregoing is merely preferred embodiment of the present disclosure, are not limited to the disclosure, for the skill of this field For art personnel, the disclosure can have various modifications and variations.It is all within the spirit and principle of the disclosure, it is made any to repair Change, equivalent replacement, improvement etc., should be included within the protection scope of the disclosure.

Claims (10)

1. a kind of orthosilicate base deep ultraviolet long after glow luminous material, characterized in that including matrix, active ions and codope from Son, the matrix are Ln2SiO5, one of Ln Lu, Y, Gd or two kinds, active ions Pr3+, co-dopant ions Li+、Na+Or K+One of.
2. orthosilicate base deep ultraviolet long after glow luminous material as described in claim 1, characterized in that Pr3+Doping concentration For 0.1%mol~5%mol;
Or, the doping concentration of co-dopant ions is 0%mol~5%mol, and the doping concentration of co-dopant ions is not 0.
3. a kind of preparation method of orthosilicate base deep ultraviolet long after glow luminous material of any of claims 1 or 2, feature It is, using Ln salt, praseodymium salt and alkali metal salt as raw material, forerunner to be obtained by sol-gal process using citric acid and ethyl orthosilicate Soma gel calcines presoma xerogel, obtains orthosilicate base deep ultraviolet long after glow luminous material, the Ln salt packet Containing Lu3+、Y3+、Gd3+One of or two kinds, the alkali metal salt include Li+、Na+Or K+One of.
4. preparation method as claimed in claim 3, characterized in that Ln3+、Pr3+Integral molar quantity and the molar ratio of citric acid be 1:1~3;Preferably, Ln3+、Pr3+Integral molar quantity and citric acid molar ratio be 1:2.
5. preparation method as claimed in claim 3, characterized in that the calcination process is not higher than 900 DEG C progress of first heating Pre-burning is then heated to and is sintered not less than 1100 DEG C;
Or, calcining carries out in air atmosphere.
6. preparation method as claimed in claim 5, characterized in that carry out tabletting after pre-burning, be then sintered;
Or, first being ground after pre-burning, tabletting is being carried out, is then being sintered.
7. preparation method as claimed in claim 5, characterized in that calcined temperature be 700~900 DEG C, burn-in time be 1~ 3h;Preferably, calcined temperature is 790~810 DEG C, and burn-in time is 1.9~2.1h;
Or, sintering temperature is 1100~1300 DEG C, sintering time is 4~8h;Preferably, sintering temperature is 1245~1255 DEG C, Sintering time is 5.9~6.1h.
8. preparation method as claimed in claim 3, characterized in that step are as follows:
(1) Ln salt, praseodymium salt and alkali metal salt are dissolved and obtains salting liquid;
(2) citric acid is added into salting liquid and is uniformly mixed acquisition mixed liquor;
(3) ethyl orthosilicate is added into mixed liquor, heating reaction obtains precursor sol;
(4) continue heating to precursor sol to be dried, obtain presoma xerogel;
(5) presoma xerogel is sintered, obtains orthosilicate base deep ultraviolet long after glow luminous material.
9. preparation method as claimed in claim 8, characterized in that the solution of step (1) is the mixed solution of ethyl alcohol and water;It is excellent Choosing, the volume ratio of ethyl alcohol and water is 3.9~4.1;
Or, the temperature dissolved in step (1) is 65~75 DEG C;
Or, the temperature dissolved in step (2) is 65~75 DEG C;
Or, the reaction temperature of step (3) is 65~75 DEG C, the reaction time is 4~6h;
Or, step (4) drying temperature is 95~105 DEG C, drying time is 12~16h;
Or, the process of step (5) are as follows: carry out pre-burning in low temperature oven after the grinding of presoma xerogel, the powder after pre-burning passes through After regrinding simultaneously tabletting, it is put into high temperature furnace, is sintered and cooled in air atmosphere.
10. a kind of orthosilicate base deep ultraviolet long after glow luminous material of any of claims 1 or 2 day blind ultraviolet imagery, light It is catalysis, disinfection and sterilization, anti-fake and/or prepare application in medical optical dynamic therapy reagent.
CN201910403086.5A 2019-05-15 2019-05-15 A kind of orthosilicate base deep ultraviolet long after glow luminous material and preparation method thereof CN110028966A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910403086.5A CN110028966A (en) 2019-05-15 2019-05-15 A kind of orthosilicate base deep ultraviolet long after glow luminous material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910403086.5A CN110028966A (en) 2019-05-15 2019-05-15 A kind of orthosilicate base deep ultraviolet long after glow luminous material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN110028966A true CN110028966A (en) 2019-07-19

Family

ID=67242221

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910403086.5A CN110028966A (en) 2019-05-15 2019-05-15 A kind of orthosilicate base deep ultraviolet long after glow luminous material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110028966A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1420154A (en) * 2001-11-20 2003-05-28 株式会社日立制作所 Phosphor and image forming device therewith
CN101140846A (en) * 2006-09-06 2008-03-12 株式会社日立显示器 Image display device
CN102399553A (en) * 2011-12-14 2012-04-04 沈阳化工大学 Ca2MgSiO5:Eu,Ce green fluorescent powder and preparation method thereof
CN102503549A (en) * 2011-11-02 2012-06-20 上海大学 Preparation method for polycrystalline thin film made of lutecium silicate doped with rare earth ions
CN104736661A (en) * 2012-10-23 2015-06-24 浜松光子学株式会社 Target for ultraviolet light generation, electron beam-excited ultraviolet light source, and production method for target for ultraviolet light generation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1420154A (en) * 2001-11-20 2003-05-28 株式会社日立制作所 Phosphor and image forming device therewith
CN101140846A (en) * 2006-09-06 2008-03-12 株式会社日立显示器 Image display device
CN102503549A (en) * 2011-11-02 2012-06-20 上海大学 Preparation method for polycrystalline thin film made of lutecium silicate doped with rare earth ions
CN102399553A (en) * 2011-12-14 2012-04-04 沈阳化工大学 Ca2MgSiO5:Eu,Ce green fluorescent powder and preparation method thereof
CN104736661A (en) * 2012-10-23 2015-06-24 浜松光子学株式会社 Target for ultraviolet light generation, electron beam-excited ultraviolet light source, and production method for target for ultraviolet light generation

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
EZRA L.CATES等: "Converting Visible Light into UVC: Microbial Inactivation by Pr3þ-Activated Upconversion Materials", 《ENVIRONMENTAL SCIENCE & TECHNOLOGY》 *
EZRA L.CATES等: "Delineating Mechanisms of Upconversion Enhancement by Li+ Codoping in Y2SiO5:Pr3+", 《J.PHYS.CHEM.C》 *
EZRA L.CATES等: "Upconversion under polychromatic excitation: Y2SiO5:Pr3+, Li+ converts violet, cyan, green, and yellow light into UVC", 《OPTICAL MATERIALS》 *
JIANHONG WU等: "Synthesis and characterization of UV upconversion material Y2SiO5:Pr3+, Li+/TiO2 with enhanced the photocatalytic properties under a xenon lamp", 《RSC ADVANCES》 *
刘成等: "Li+掺杂对Y2SiO5:Pr3+上转换发光性能影响", 《中国稀土学报》 *

Similar Documents

Publication Publication Date Title
Wong et al. Towards pure near-infrared to near-infrared upconversion of multifunctional GdF 3: Yb 3+, Tm 3+ nanoparticles
Zhang et al. Hydroxyapatite nano-and microcrystals with multiform morphologies: controllable synthesis and luminescence properties
Yang et al. Magnetic and upconverted luminescent properties of multifunctional lanthanide doped cubic KGdF 4 nanocrystals
Diaz-Torres et al. Efficient photoluminescence of Dy3+ at low concentrations in nanocrystalline ZrO2
Guo et al. Luminescent properties of R2 (MoO4) 3: Eu3+ (R= La, Y, Gd) phosphors prepared by sol–gel process
EP2412691B1 (en) Use of fluorescent zirconia material as dental material
Sokolnicki et al. Synthesis and spectroscopic investigations of Sr2Y8 (SiO4) 6O2: Eu2+, Eu3+ phosphor for white LEDs
CN103421511B (en) Bismuth oxyhalide light-emitting material with doped rare earth ions and preparation method thereof
Singh et al. Luminescence and defect centres in MgSrAl10O17: Sm3+ phosphor
Bai et al. Enhanced white light emission in Er/Tm/Yb/Li codoped Y2O3 nanocrystals
TW200838984A (en) Aluminum-silicate based orange-red phosphors with mixed divalent and trivalent cations
WO2006113998A1 (en) Production of light from sol-gel derived thin films made with lanthanide doped nanoparticles, and preparation thereof
TW200909564A (en) Silicate-base luminescent material with muti-emission peak, a method of manufacturing the same and a lighting apparatus using the same
CN105219387B (en) A kind of metatitanic acid alkali red illuminating material of additive Mn and its preparation method and application
CN105419799B (en) The preparation method and applications of the material of black light switching emission red fluorescence
CN101974334B (en) Single-phase rare earth vanadium phosphate white fluorescent powder for mercury lamp and preparation method thereof
CN103113892B (en) A kind of tungstate rare earth light conversion material, preparation method and application
CA2520035C (en) Single-component, uv-emitting phosphor
Lim Upconversion photoluminescence properties of SrY2 (MoO4) 4: Er3+/Yb3+ phosphors synthesized by a cyclic microwave-modified sol–gel method
CN101177611A (en) High luminous intensity up-conversion fluorescence nano-crystal oxide and preparation method thereof
Xu et al. Photoluminescence characteristics of energy transfer between Er3+ and Bi3+ in Gd2O3: Er3+, Bi3+
CN102618270B (en) A kind of white light LEDs vanadate substrate fluorescent powder and preparation method thereof
Dejene et al. Structural and photoluminescence properties of Dy3+ co-doped and Eu2+ activated MAl2O4 (M= Ba, Ca, Sr) nanophosphors
CN102994089A (en) Preparation method of alkaline earth fluoride nanocrystal with ultra small core-shell structure
CN104910909B (en) Erbium-doped lanthanum titanate fluorescent compound, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination