CN104556692B - PbSe quantum dot doped germanate glass and preparation method thereof - Google Patents
PbSe quantum dot doped germanate glass and preparation method thereof Download PDFInfo
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- CN104556692B CN104556692B CN201410787872.7A CN201410787872A CN104556692B CN 104556692 B CN104556692 B CN 104556692B CN 201410787872 A CN201410787872 A CN 201410787872A CN 104556692 B CN104556692 B CN 104556692B
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Abstract
The invention discloses PbSe quantum dot doped germanate glass capable of realizing wide spectrum (1.2-2.0 microns) fluorescence. The PbSe quantum dot doped germanate glass consists of the following components in molar ratio: 45-60% of GeO2, 5-10% of Na2CO3, 15-30% of BaF2, 5-15% of Al2O3, 0.5-3% of ZnSe and 0.4-2% of PbO. A preparation method of the glass comprises the following steps: weighing an appropriate amount of components according to the molar ratios, putting the components into a ball-milling sample mixing machine, mixing fully and uniformly, then putting the mixture into a semi-sealed corundum crucible provided with a cover, melting in a high-temperature electric resistance furnace at 1350-1400 DEG C for 30-60 minutes, then quickly cooling for forming, and quickly transferring into an annealing furnace at 360 DEG C to perform heat preservation for 3 hours so as to eliminate residual stress, thereby obtaining yellow transparent glass; and treating at 500-530 DEG C for 10-20 hours to obtain PbSe quantum dot doped black glass. The PbSe quantum dot doped germanate glass has relatively high transmittance in a near/middle infrared wave band, and has good fluorescence property in the near/middle infrared wave band.
Description
Technical field
The present invention relates to information functional material field, the quantum dot-doped germanate glass of more particularly, to a kind of pbse and its system
Preparation Method.
Background technology
The essence of quantum dot is a kind of semiconductor nanoparticle of standard zero dimension, and in general its particle diameter is less than exciton Bohr
Radius, the motion of the carrier in quantum dot is in strong constrained state, continuous band structure become have molecular characterization point
Vertical level structure, can launch fluorescence after being excited.Semiconductor quantum in material is pressed the situation that the different same clans be combined with each other and can be divided
For several as follows: ib-viia (cucl, cubr, agbr etc.), iib-via (cds, cdse, zns, cdte etc.)；iiia-va
(gaas, inas etc.)；Iva-via (pbs, pbse etc.)；va-via(bi2s3Deng).Wherein iva-via race semi-conducting material has
Less band gap and larger exciton Bohr radius (if pbs is 18nm, pbse is 46nm), therefore iva-via race quantum dot has
Effect band gap adjustable extent is big, is capable of adjustable absorption and the radiation of nearly middle-infrared band in theory.Quantum dot application study is near
Obtain many progress over year, particularly use it for the research of doped-glass.But, how to obtain iva-via race quantum dot and mix
Miscellaneous glass material is simultaneously realized glass and is lighted in nearly mid-infrared the focus of always this skilled person research.
Content of the invention
It is an object of the invention to provide quantum dot-doped germanate glass of a kind of pbse and preparation method thereof.It prepares work
Skill is simple, and quantum dot size is controlled, and low cost is it is adaptable to laser glass and fiber optic materials field.
The present invention by solving the scheme that above-mentioned technical problem is adopted is:
A kind of quantum dot-doped germanate glass of pbse is it is characterised in that the quantum dot-doped germanate glass of described pbse
It is made up of the raw material of following molar percentage: geo2: 45～60%, na2co3: 5～10%, baf2: 15～30%, al2o3: 5
～15%, znse:0.5～3%, pbo:0.4～2%.
In such scheme, the quantum dot-doped germanate glass of described pbse is made up of the raw material of following molar percentage:
geo2: 57.69%, na2co3: 9.62%, baf2: 19.23%, al2o3: 9.62%, znse:1.92%, pbo:1.92%.
In such scheme, the quantum dot-doped germanate glass of described pbse is made up of the raw material of following molar percentage:
geo2: 52.38%, na2co3: 9.52%, baf2: 23.82%, al2o3: 9.52%, znse:2.86%, pbo:1.90%.
In such scheme, the quantum dot-doped germanate glass of described pbse is made up of the raw material of following molar percentage:
geo2: 48.54%, na2co3: 9.71%, baf2: 29.13%, al2o3: 9.71%, znse:1.94%, pbo:0.97%.
In such scheme, the quantum dot-doped germanate glass of described pbse is made up of the raw material of following molar percentage:
geo2: 49.26%, na2co3: 9.85%, baf2: 24.63%, al2o3: 14.78%, znse:0.99%, pbo:0.49%.
In such scheme, the quantum dot-doped germanate glass of described pbse is made up of the raw material of following molar percentage:
geo2: 49.5%, na2co3: 9.9%, baf2: 24.76%, al2o3: 14.85%, znse:0.59%, pbo:0.40%.
The preparation method of the quantum dot-doped germanate glass of described pbse is it is characterised in that the method is will be all former
Material is placed in ball milling sample mixing machine after weighing according to molar percentage and fully mixes, and is placed in the corundum crucible added a cover, at 1350 DEG C
30min～60min is founded, then rapid shaping cooling, puts into annealing 3h in 360 DEG C of stove, obtain yellow at～1400 DEG C
Clear glass, is heat-treated to prepared yellow transparent glass, obtains the quantum dot-doped germanate glass of pbse of black.
In such scheme, described crucible is the crucible added a cover.
In such scheme, described heat treatment condition is insulation 10～20h at 500 DEG C～530 DEG C.
The present invention adopts fusion method to prepare the quantum dot-doped germanate glass of pbse, in its raw material composition, geo2For glass
Form body, its constituent content must be poor less than this scope glass glass forming ability in the range of 45～60%, and not easy-formation, higher than this
Then se solubility in glass matrix is excessive for scope, the precipitation of unfavorable pbse quantum dot.al2o3For glass intermediate, na2co3With
baf2Network outer body.Znse and pbo is then that the presoma as pbse quantum dot introduces se element and pb element respectively.na2co3
And baf2Introducing purpose, one is the fusing point reducing glass to a certain extent.We study discovery in early days, and se is in germanate glass
Solubility in glass matrix is larger, fluoride be introduced into the solubility that can reduce se in glass matrix, thus be more easy to separate out
Pbse quantum dot, two is by introducing a certain amount of network outer body in the form of fluoride, can weaken glass to a certain extent
The effect of internal hydroxyl groups.From germanate glass matrix as quantum dot carrier, be because germanate glass is in mid-infrared ripple
The relatively high permeability of section, provides prerequisite for realizing quantum dot-doped glass in the application of middle-infrared band, this is also this
Bright maximum advantage compared with other quantum dot doped-glasses, is also its innovation.
The invention has the beneficial effects as follows:
1) present invention is successfully prepared pbse quantum dot by fusion method first in germanate glass matrix, and by not
The size that same Technology for Heating Processing can realize quantum dot is controlled, thus reaching the effective fluorescence between 1.2～2.0 μm.Tradition
Silicate glass limits pbse quantum dot fluorescence efficiency with narrower through spectrum due to its higher phonon energy, thus affecting it
Mid-infrared luminous.Germanate glass has the advantages that phonon energy is low and glass forming ability is good, and introduces fluorine in glass ingredient
Compound, can weaken the effect of inside glass hydroxyl to a certain extent, reduce the suction of the hydroxyl at 3.0 μm about places for the glass
Receive, thus for realizing glass and lighting in mid-infrared providing possible condition.
2) the quantum dot-doped germanate glass of pbse is at home and abroad all rarely reported.Because germanate glass becomes glass relatively
Good, can combine thus preparing quantum dot fiber amplifier with existing preform drawing technology.
Brief description
Fig. 1 is the near-infrared absorption spectrum of the quantum dot-doped germanate glass of pbse that the embodiment of the present invention 1 to 5 is obtained
Figure.Wherein, ap sample is not thermally treated pristine glass sample.Can be seen that by glass ingredient from absorption spectrum in figure
And the regulation and control of Technology for Heating Processing, it is possible to achieve the quantum dot-doped germanate glass of pbse is in the adjustable suction of near, middle-infrared band
Receive.
Fig. 2 is the fluorescence spectra of the quantum dot-doped germanate glass of pbse that the embodiment of the present invention 1 to 5 is obtained.From glimmering
Can be seen that by the regulation and control to glass ingredient and Technology for Heating Processing in light spectrogram, it is possible to achieve the quantum dot-doped germanium of pbse
Silicate glass wide spectrum fluorescence between 1.2～2.0 μm, its maximum fluorescence peak width (fwhm) can reach 403nm.
Specific embodiment
Below in conjunction with drawings and Examples, the present invention will be described further, but present disclosure is not limited solely to
The following examples.
Table 1 gives the glass ingredient of the embodiment of the present invention 1 to 5.
The glass ingredient of table 1 embodiment 1 to 5
| Component (mol%) | geo2 | na2co3 | baf2 | al2o3 | znse | pbo |
| Embodiment 1 (s1) | 57.69 | 9.62 | 19.23 | 9.62 | 1.92 | 1.92 |
| Embodiment 2 (s2) | 52.38 | 9.52 | 23.82 | 9.52 | 2.86 | 1.90 |
| Embodiment 3 (s3) | 48.54 | 9.71 | 29.13 | 9.71 | 1.94 | 0.97 |
| Embodiment 4 (s4) | 49.26 | 9.85 | 24.63 | 14.78 | 0.99 | 0.49 |
| Embodiment 5 (s5) | 49.50 | 9.90 | 24.76 | 14.85 | 0.59 | 0.40 |
Embodiment 1
S1 component molar ratio weighs geo respectively as described above2: 15g；na2co3: 2.53g；baf2: 8.38g；al2o3:
2.44g；Znse:0.69g；Pbo:1.07g.After fully mixing in ball milling sample mixing machine, it is placed in and adds a cover in corundum crucible 1350
Found 30min at DEG C and then with steel plate compressing cooling rapidly, put into annealing 3h in 360 DEG C of stove, obtain yellow transparent
Glass.Can be seen that its pristine glass (No. 1 curve of Fig. 1) from absorption spectrum in figure all not having near infrared band in visible ray
There is absworption peak., after processing 10 hours at 510 DEG C, absworption peak, its fluorescence peak position exists at 1385nm in sample
At 1434nm, its Absorption and fluorescence spectrum is respectively as depicted in figs. 1 and 2.
Embodiment 2
S2 component molar ratio weighs geo respectively as described above2: 15g；na2co3: 2.76g；baf2: 11.43g；al2o3:
2.66g；Znse:1.13g；Pbo:1.16g.After fully mixing in ball milling sample mixing machine, it is placed in and adds a cover in corundum crucible 1350
Found 30min at DEG C and then with steel plate compressing cooling rapidly, put into annealing 3h in 360 DEG C of stove, obtain yellow transparent
Glass.From abosrption spectrogram as can be seen that its pristine glass (No. 10 curves of Fig. 1) does not all have near infrared band in visible ray
Absworption peak.Sample is processed after processing 10h at 10 and 20 hours, and 530 DEG C at 510 DEG C, respectively in 1269nm, 1474nm
And at 1631nm, absworption peak occurs, its fluorescence peak position respectively at 1313nm, 1558nm and 1684nm, its absorption spectrum
With fluorescence spectrum respectively as depicted in figs. 1 and 2.
Embodiment 3
S3 component molar ratio weighs geo respectively as described above2: 10g；na2co3: 2.03g；baf2: 10.06g；al2o3:
1.95g；Znse:0.55g；Pbo:0.43g.With being sufficiently mixed in ball milling sample mixing machine after uniformly, be placed in add a cover in corundum crucible
Found 30min at 1350 DEG C and then with steel plate compressing cooling rapidly, put into annealing 3h in 360 DEG C of stove, obtain yellow
Clear glass.From abosrption spectrogram as can be seen that its pristine glass (No. 7 curves of Fig. 1) in visible ray near infrared band all
There is no absworption peak.Sample processes 10 hours at 510 DEG C and processes 10h at 530 DEG C, respectively at 1343nm and 1658
Absworption peak occurs, its fluorescence peak position, respectively at 1506nm and 1744nm, processes the sample of 10h at 530 DEG C, its fluorescence peak
Fwhm value can reach 403nm, and its Absorption and fluorescence spectrum is respectively as depicted in figs. 1 and 2.
Embodiment 4
S4 component molar ratio weighs geo respectively as described above2: 10g；na2co3: 2.03g；baf2: 8.38g；al2o3:
2.92g；Znse:0.28g；Pbo:0.21g.After fully mixing in ball milling sample mixing machine, it is placed in and adds a cover in corundum crucible 1350
Found 30min at DEG C and then with steel plate compressing cooling rapidly, put into annealing 3h in 360 DEG C of stove, obtain yellow transparent
Glass.From abosrption spectrogram as can be seen that its pristine glass (No. 3 curves of Fig. 1) does not all have near infrared band in visible ray
Absworption peak.Sample is processed 10 hours although not observing obvious absworption peak at 500 DEG C, but bent with the absorption of original sample
Line contrasts, and it has obvious absorption near infrared band, its fluorescence peak position at 1299nm, its Absorption and fluorescence spectrum
Respectively as depicted in figs. 1 and 2.
Embodiment 5
S5 component molar ratio weighs geo respectively as described above2: 10g；na2co3: 2.03g；baf2: 8.38g；al2o3:
2.92g；Znse:0.16g；Pbo:0.17g.After fully mixing in ball milling sample mixing machine, it is placed in and adds a cover in corundum crucible 1350
Found 30min at DEG C and then with steel plate compressing cooling rapidly, put into annealing 3h in 360 DEG C of stove, obtain yellow transparent
Glass.From abosrption spectrogram as can be seen that its pristine glass (No. 5 curves of Fig. 1) does not all have near infrared band in visible ray
Absworption peak.Sample is processed 10 hours at 500 DEG C, and its absworption peak occurs in 1304nm, its fluorescence peak position at 1393nm,
Its Absorption and fluorescence spectrum is respectively as depicted in figs. 1 and 2.
Claims (8)
1. a kind of quantum dot-doped germanate glass of pbse is it is characterised in that the quantum dot-doped germanate glass of described pbse is
It is made up of the raw material of following molar percentage: geo2: 45～60%, na2co3: 5～10%, baf2: 15～30%, al2o3: 5～
15%, znse:0.5～3%, pbo:0.4～2%.
2. the quantum dot-doped germanate glass of pbse as claimed in claim 1 is it is characterised in that described pbse is quantum dot-doped
Germanate glass is made up of the raw material of following molar percentage: geo2: 57.69%, na2co3: 9.62%, baf2:
19.23%, al2o3: 9.62%, znse:1.92%, pbo:1.92%.
3. the quantum dot-doped germanate glass of pbse as claimed in claim 1 is it is characterised in that described pbse is quantum dot-doped
Germanate glass is made up of the raw material of following molar percentage: geo2: 52.38%, na2co3: 9.52%, baf2:
23.82%, al2o3: 9.52%, znse:2.86%, pbo:1.90%.
4. the quantum dot-doped germanate glass of pbse as claimed in claim 1 is it is characterised in that described pbse is quantum dot-doped
Germanate glass is made up of the raw material of following molar percentage: geo2: 48.54%, na2co3: 9.71%, baf2:
29.13%, al2o3: 9.71%, znse:1.94%, pbo:0.97%.
5. the quantum dot-doped germanate glass of pbse as claimed in claim 1 is it is characterised in that described pbse is quantum dot-doped
Germanate glass is made up of the raw material of following molar percentage: geo2: 49.26%, na2co3: 9.85%, baf2:
24.63%, al2o3: 14.78%, znse:0.99%, pbo:0.49%.
6. the quantum dot-doped germanate glass of pbse as claimed in claim 1 is it is characterised in that described pbse is quantum dot-doped
Germanate glass is made up of the raw material of following molar percentage: geo2: 49.5%, na2co3: 9.9%, baf2: 24.76%,
al2o3: 14.85%, znse:0.59%, pbo:0.40%.
7. the preparation method of the quantum dot-doped germanate glass of pbse as claimed in claim 1 is it is characterised in that the method is
It is placed on after all raw materials are weighed according to molar percentage in ball milling sample mixing machine and fully mixes, be placed in the corundum crucible added a cover,
Found 30min～60min at 1350 DEG C～1400 DEG C, then rapid shaping cooling, puts into annealing 3h in 360 DEG C of stove,
Obtain yellow transparent glass, prepared yellow transparent glass is heat-treated, obtain the quantum dot-doped germanic acid of pbse of black
Salt glass.
8. the preparation method of the quantum dot-doped germanate glass of pbse as claimed in claim 7 is it is characterised in that at described heat
Manage bar part is insulation 10～20h at 500 DEG C～530 DEG C.
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| CN108585527A (en) * | 2018-05-16 | 2018-09-28 | 武汉理工大学 | A kind of Pb1-xSrxSe ternary quantum dots doped-glasses and preparation method thereof |
| CN108519714A (en) * | 2018-06-27 | 2018-09-11 | 浙江工业大学 | A kind of sodium Boroalumino silicate glasses near-infrared broadband PbSe quantum dot light fiber amplifiers |
| CN112340997A (en) * | 2020-10-09 | 2021-02-09 | 武汉理工大学 | PbSe quantum dot doped lithium aluminum silicon glass ceramic with efficient near-infrared luminescence, and preparation method and application thereof |
| CN114735933B (en) * | 2022-04-12 | 2023-11-14 | 中国计量大学上虞高等研究院有限公司 | Broadband luminescent ZnSe quantum dot glass and preparation method and application thereof |
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