CN106946456A - A kind of CdS quantum dot doped-glass and preparation method thereof - Google Patents
A kind of CdS quantum dot doped-glass and preparation method thereof Download PDFInfo
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- CN106946456A CN106946456A CN201710297214.3A CN201710297214A CN106946456A CN 106946456 A CN106946456 A CN 106946456A CN 201710297214 A CN201710297214 A CN 201710297214A CN 106946456 A CN106946456 A CN 106946456A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
Abstract
The present invention provides a kind of CdS quantum dot doped-glass, and described glass basic composition is：SiO2：50~58mol%；CaO and/or BaO：15 20mol%；Na2O：14~20mol%；Al2O3：3 8mol%；ZnO and/or ZnS：0.5 11.5mol%, said components sum is 100%；The composition of the glass also includes the CdS and/or CdO for accounting for 0.1~2.0mol% of said components sum；Wherein CdS and ZnS total amount constitutes the 4% of component total mole number substantially no more than glass.The method for glass preparation is：Be well mixed after each component by mole being weighed, postforming is melted at high temperature and is annealed；CdS quantum dot is prepared by being further heat-treated in glass matrix.Quantum dot-doped glass prepared by the present invention has good chemical stability, and higher fluorescence quantum efficiency is a kind of semiconductor nano luminescent material of great application prospect.
Description
Technical field
The present invention relates to field of light emitting materials, more particularly to a kind of CdS quantum dot doped-glass and preparation method thereof.
Background technology
Because the skin effect of quantum dot, quantum confined effect and dimensional effect so that it has a series of large scales brilliant
Special performance not available for body material, so as to cause extensive concern.After 2000, the raising of quantum dot technology of preparing
The spectrum of the development of its application field, especially technology of quantum dots has been driven with size adjustable, Stokes shift be big, luminous effect
Rate is high, stability of photoluminescence is good etc., and a series of unique optical properties are even more to turn into the focus of Recent study, and are achieved great
Progress.
Because the characteristic that quantum dot possesses, various countries researcher expands substantial amounts of research work for quantum dot.Ⅱ-Ⅵ
Race's quantum dot such as CdS, CdTe, CdSe etc. have wider band-gap energy, and energy gap changes greatly, with powerful application prospect.
The energy gap of CdS quantum dot is~2.52ev, and its intrinsic emission wavelength range is general in 300~510nm.Glass preparation technique
Simply, low cost, is a kind of with the good transparency, mechanical stability, chemical stability compared to other crystalline materials
Good matrix material.Also, quantum dot, which is doped into glass, can prevent the reunion of quantum dot, good chemically stable is obtained
Property, play good encapsulation effect.
The preparation method of current CdS quantum dot mainly has sol-gal process and traditional high-temperature fusion-heat treating process.Compare
In sol-gal process, doped quantum dot is not easy to follow-up surface treatment, quantum dot surface and glass basis interface in glass
There are many defects, these defects are very capable for the capture in electronics and hole, so that the luminous of exciton state greatly subtracts
Weak, intrinsic light seems very faint compared to the luminous of defect state.Patent of invention ZL201410787871.2 discloses a kind of energy
Enough realize that the intrinsic luminous glass of CdSe quantum dot is constituted, but the glass composition according to the patent and preparation method thereof, it is impossible to make
It is standby that there is intrinsic luminous CdS quantum dot.Its main cause is the chemical property and diffusivity of S and Se in glass matrix, melted
Melt retention abilities of the S from Se in glass matrix in preparation process different.
The content of the invention
It can realize that stronger quantum dot is intrinsic luminous with wide spectrum defect luminescence it is an object of the invention to provide a kind of
CdS quantum dot doped-glass and preparation method thereof.The luminescent properties of the CdS quantum dot doped-glass are excellent, and quantum efficiency is high, amount
The ratio of son point intrinsic luminous intensity and defect luminescence intensity is adjustable.
The present invention be solve the scheme that is used of above-mentioned technical problem for：
A kind of CdS quantum dot doped-glass, described glass basic composition is：SiO2：50~58mol%；CaO and/
Or BaO：15-20mol%；Na2O：14~20mol%；Al2O3：3-8mol%；ZnO and/or ZnS：0.5-11.5mol%, on
It is 100% to state component sum；The glass composition also include account for said components sum 0.1~2.0mol% CdS and/or
CdO；Wherein CdS and ZnS total amount constitutes the 4% of component total mole number substantially no more than glass.
In such scheme, the fluorescence of the CdS quantum dot generated in glass includes the intrinsic luminous and wide range of quantum dot
Defect luminescence, and the ratio of intrinsic luminous intensity and defect luminescence intensity is adjustable.
In such scheme, the incorporation way of S elements is for the incorporation way of ZnS or CdS, Cd element in the glass composition
CdO or CdS.
In such scheme, the molal quantity of sulphur is higher than the molal quantity of cadmium in the glass composition.
In such scheme, the method for glass preparation is：Be well mixed after each component by mole being weighed, at high temperature
Melting postforming is simultaneously annealed；CdS quantum dot is prepared by being further heat-treated in glass matrix.
In such scheme, the intrinsic emission wavelength of the CdS quantum dot continuously adjustabe in the range of 400~520nm；Glass matrix
Middle CdS quantum dot defect luminescence covers 500~650nm scopes.
In such scheme, the composition of the CdS quantum dot doped-glass is：SiO2：50mol%；CaO：9mol%；BaO：
8mol%；Na2O：20mol%；Al2O3：5mol%；ZnO：8mol%, and 1mol% CdS is additionally added, heat treating regime is
530~590 DEG C of processing 10h.With the rise of heat treatment temperature, the ratio of intrinsic luminous peak intensity and defect luminescence intensity exists
It can regulate and control in the range of 429nm~454nm.
In such scheme, the composition of the CdS quantum dot doped-glass is：SiO2：53mol%；CaO：9mol%；BaO：
8mol%；Na2O：20mol%；Al2O3：5mol%；ZnO：3.5mol%；ZnS：1.5mol%, and additionally add 1mol%'s
CdO, heat treating regime is 550~610 DEG C of processing 10h.With the rise of heat treatment temperature, intrinsic luminous peak intensity and defect hair
The ratio of luminous intensity can regulate and control in the range of 446nm~525nm.
The thinking of the present invention is that appropriate CdS or CdO and ZnS is added in silicate systems glass, is turned higher than glass
Temperature and temperature range less than recrystallization temperature are heat-treated to glass, CdS quantum dot is separated out from glass basis；It is logical
Regulation and control heat treating regime is crossed, various sizes of quantum dot is obtained.Also, after CdS quantum dot is separated out, ZnS can be in quantum dot
Surface separates out to form shell passivated surface defect, realizes defect luminescence and intrinsic luminous intensity controllable.
The role of each raw material of the present invention：SiO2For Network former, [SiO4] it is the basic of silicate glass system
Composition；Na2O, CaO and BaO are network outer body, are the suppliers of free oxygen, play suspension, Na2O is also as fluxing agent, reduction
The viscosity and surface tension of glass metal；Al2O3It is intermediate oxide, Al with ZnO2O3The tendency towards devitrification of glass, ZnO can be reduced
The formation of quantum dot can be promoted, and reduce the volatilization of sulphur.CdS or CdO and ZnS is the introducing body of CdS quantum dot.
One of key problem in technology of the present invention is that the introducing of alkaline earth oxide (CaO+BaO) in glass matrix can be carried
The retention ability of S elements in high prepared glass.
The two of the key problem in technology of the present invention are CdS quantum dot growth size controllables in glass, and surface defect can be blunt
Change, so as to realize the intrinsic continuously adjustabe lighted in the range of 350~500nm of quantum dot.In certain temperature range, heat treatment
Temperature is higher, and heat treatment time is longer, and quantum dot size is bigger.
In summary, the present invention improves staying in the glass matrix of S elements by introducing alkaline-earth metal in glass matrix
Deposit ability；And the adjustment of alkali metal concn is combined, the diffusivity of S elements in glass matrix is improved, promotes the analysis of CdS quantum dot
Crystalline substance, and the S elements by being had more than needed in glass matrix, realize the partial deactivation of CdS quantum dot surface defect in glass matrix, so that
Realize that the intrinsic of CdS quantum dot lights in glass matrix.
The beneficial effects of the invention are as follows：Controllability of the present invention is strong, and product is homogeneous, stably；Technique is simple, simple to operate, into
This is cheap, can produce in batches；Prepared CdS quantum dot doped-glass performance is stable, defect luminescence and intrinsic luminous ratio
Adjustable, the high-quantum efficiency for resulting in specific wavelength in certain limit lights, and can be applied to solar cell, LED, quantum dot
The fields such as laser, fiber amplifier.
Brief description of the drawings
Fig. 1, Fig. 2 are respectively the Absorption and fluorescence spectrum of embodiment 1；
Fig. 3, Fig. 4 are respectively the Absorption and fluorescence spectrum of embodiment 2；
Fig. 5, Fig. 6 are respectively the Absorption and fluorescence spectrum of embodiment 3；
Fig. 7, Fig. 8 are respectively the Absorption and fluorescence spectrum of embodiment 4；
Fig. 9, Figure 10 are respectively the Absorption and fluorescence spectrum of embodiment 5；
Figure 11, Figure 12 are respectively the Absorption and fluorescence spectrum of embodiment 6；
Figure 13, Figure 14 are respectively the Absorption and fluorescence spectrum of embodiment 7；
Figure 15, Figure 16 are respectively the Absorption and fluorescence spectrum of embodiment 8；
Figure 17, Figure 18 are respectively the Absorption and fluorescence spectrum of embodiment 9.
Embodiment
Below in conjunction with drawings and Examples, further the present invention will be described, but present disclosure is not limited solely to
The following examples.
Embodiment 1
The glass composition of the present embodiment is SiO2：58mol%；CaO：9mol%；BaO：7.5mol%；Na2O：20mol%；
Al2O3：5mol%；ZnO：0.5mol%, and additionally add 1mol% CdS.Frit selects SiO2：Na2CO3、CaCO3、
BaCO3、Al2O3、ZnO、CdS.Each component is weighed by above-mentioned molar percentage, is placed in batch mixer and is well mixed, be placed in after taking-up
In closed corundum crucible, it is then placed in electric furnace and melts 40min at 1350 DEG C, be then poured over melt on metal copper mold soon
Fast quenching shaping, is put into annealing furnace the 2h that annealed at 300 DEG C, obtains pristine glass after furnace cooling, be designated as C1, be cut into spy
Fixed size, for being heat-treated.
Then pristine glass is placed in heat-treatment furnace, respectively in 550 DEG C, 570 DEG C, 590 DEG C, 610 DEG C of heat treatment 10h,
Furnace cooling obtains CdS quantum dot silicate glass sample to room temperature, and absorption spectrum is as shown in Figure 1.C1-AP is represented without heat
The pristine glass sample of processing, 550 DEG C/10h represents that the rest may be inferred to glass treatment 10h at 550 DEG C.Can from figure
Go out, with the rise of heat treatment temperature, ABSORPTION EDGE is not moved substantially, the sample ABSORPTION EDGE of 550 DEG C/10h heat treatments is
Through having reached 500nm, this illustrates the solubility of CdS in glass saturation, and CdS quantum can not be promoted by continuing rise temperature
The further precipitation of point；It is observed that CdS quantum dot wide range lights on fluorescence spectrum (Fig. 2).670nm is attached in fluorescence spectrum
Near glow peak recess feature is caused by tester.
Embodiment 2
The glass composition of the present embodiment is SiO2：50mol%；CaO：13mol%；BaO：4mol%；Na2O：20mol%；
Al2O3：5mol%；ZnO：8mol%, and additionally add 1mol% CdS.Frit selects SiO2：Na2CO3、CaCO3、
BaCO3、Al2O3、ZnO、CdS.Each component is weighed by above-mentioned molar percentage, is placed in batch mixer and is well mixed, be placed in after taking-up
In closed corundum crucible, it is then placed in electric furnace and melts 40min at 1350 DEG C, be then poured over melt on metal copper mold soon
Fast quenching shaping, is put into annealing furnace the 2h that annealed at 300 DEG C, obtains pristine glass after furnace cooling, be designated as C2, be cut into spy
Fixed size, for being heat-treated.
Then pristine glass is placed in heat-treatment furnace, respectively in 530 DEG C, 550 DEG C, 570 DEG C, 590 DEG C of heat treatment 10h,
Furnace cooling obtains CdS quantum dot silicate glass sample, Absorption and fluorescence spectrum is respectively such as Fig. 3, Fig. 4 institute to room temperature
Show.C2-AP represents not thermally treated pristine glass sample, and 530 DEG C/10h is represented at 530 DEG C to glass treatment 10h, according to this
Analogize.It can be seen that as the warm ABSORPTION EDGE of heat treatment is not moved substantially, the ABSORPTION EDGE of glass is in 500nm
Left and right.Observe that the wide range of CdS quantum dot lights on fluorescence spectrum.Illustrate to have formed CdS quantum dot in glass matrix.
Embodiment 3
The glass composition of the present embodiment is SiO2：50mol%；CaO：11mol%；BaO：6mol%；Na2O：20mol%；
Al2O3：5mol%；ZnO：8mol%, and additionally add 1mol% CdS.Frit selects SiO2：Na2CO3、CaCO3、
BaCO3、Al2O3、ZnO、CdS.Each component is weighed by above-mentioned molar percentage, is placed in batch mixer and is well mixed, be placed in after taking-up
In closed corundum crucible, it is then placed in electric furnace and melts 40min at 1350 DEG C, be then poured over melt on metal copper mold soon
Fast quenching shaping, is put into annealing furnace the 2h that annealed at 300 DEG C, obtains pristine glass after furnace cooling, be designated as C3, be cut into spy
Fixed size, for being heat-treated.
Then pristine glass is placed in heat-treatment furnace, respectively in 530 DEG C, 550 DEG C, 570 DEG C, 590 DEG C of heat treatment 10h,
Furnace cooling obtains CdS quantum dot silicate glass sample, Absorption and fluorescence spectrum is respectively such as Fig. 5 and Fig. 6 institutes to room temperature
Show.C3-AP represents not thermally treated pristine glass sample, and 530 DEG C/10h is represented at 530 DEG C to glass treatment 10h, according to this
Analogize.It can be seen that with the rise of heat treatment temperature, ABSORPTION EDGE is moved to long wave direction, illustrates CdS quantum dot
Formed in glass matrix.As heat treatment temperature is raised, the fluorescence of CdS quantum dot is gradually by single wide light in glass matrix
Spectrum fluorescence changes to bimodal fluorescence；Wide range fluorescence at 600nm is that the fluorescence at the defect luminescence of CdS quantum dot, 425nm is
The intrinsic of CdS quantum dot lights.
Embodiment 4
The glass composition of the present embodiment is SiO2：50mol%；CaO：9mol%；BaO：8mol%；Na2O：20mol%；
Al2O3：5mol%；ZnO：8mol%, and additionally add 1mol% CdS.Frit selects SiO2：Na2CO3、CaCO3、
BaCO3、Al2O3、ZnO、CdS.Each component is weighed by above-mentioned molar percentage, is placed in batch mixer and is well mixed, be placed in after taking-up
In closed corundum crucible, it is then placed in electric furnace and melts 40min at 1350 DEG C, be then poured over melt on metal copper mold soon
Fast quenching shaping, is put into annealing furnace the 2h that annealed at 300 DEG C, obtains pristine glass after furnace cooling, be designated as C4, be cut into spy
Fixed size, for being heat-treated.
Then pristine glass is placed in heat-treatment furnace, respectively in 530 DEG C, 550 DEG C, 570 DEG C, 590 DEG C of heat treatment 10h,
Furnace cooling obtains CdS quantum dot silicate glass sample, Absorption and fluorescence spectrum is respectively such as Fig. 7 and Fig. 8 institutes to room temperature
Show.C4-AP represents not thermally treated pristine glass sample, and 530 DEG C/10h is represented at 530 DEG C to glass treatment 10h, according to this
Analogize.It can be seen that with the rise of heat treatment temperature, ABSORPTION EDGE is moved to long wave direction.530 DEG C/10h ABSORPTION EDGEs
It is moved, illustrates the generation for having quantum dot, but do not have the intrinsic glow peak of quantum dot in fluorescence spectrum.Opened from 550 DEG C/10h
Beginning occurs in that the intrinsic glow peak (at 430nm) of CdS quantum dot, is the scarce of quantum dot positioned at 600nm or so wide in range glow peak
Fall into luminous.Heat treatment temperature is further raised, intrinsic glow peak proportion enhancing, because the surface of CdS quantum dot lacks
Fall into and be passivated.Glow peak in fluorescence spectrum at 615nm is due to that tester is caused in itself.
Embodiment 5
The glass composition of the present embodiment is SiO2：50mol%；CaO：7mol%；BaO：12mol%；Na2O：20mol%；
Al2O3：5mol%；ZnO：8mol%, and additionally add 1mol% CdS.Frit selects SiO2：Na2CO3、CaCO3、
BaCO3、Al2O3、ZnO、CdS.Each component is weighed by above-mentioned molar percentage, is placed in batch mixer and is well mixed, be placed in after taking-up
In closed corundum crucible, it is then placed in electric furnace and melts 40min at 1350 DEG C, be then poured over melt on metal copper mold soon
Fast quenching shaping, is put into annealing furnace the 2h that annealed at 300 DEG C, obtains pristine glass after furnace cooling, be designated as C5, be cut into spy
Fixed size, for being heat-treated.
Then pristine glass is placed in heat-treatment furnace, respectively in 530 DEG C, 550 DEG C, 570 DEG C, 590 DEG C of heat treatment 10h,
Furnace cooling obtains CdS quantum dot silicate glass sample, Absorption and fluorescence spectrum is respectively such as Fig. 9 and Figure 10 to room temperature
It is shown.C5-AP represents not thermally treated pristine glass sample, and 530 DEG C/10h is represented at 530 DEG C to glass treatment 10h, according to
This analogizes.It can be seen that with the rise of heat treatment temperature, ABSORPTION EDGE is moved to long wave direction.530 DEG C/10h absorbs
While being moved, illustrate the generation for having quantum dot, but there is no the intrinsic glow peak of quantum dot in fluorescence spectrum.From 550 DEG C/10h
Start to occur in that the intrinsic glow peak (near 470nm) of CdS quantum dot, 550-700nm wide in range glow peak lacking for quantum dot
Fall into luminous, but its intensity has been greatly reduced, because the surface defect of CdS quantum dot is passivated.In fluorescence spectrum
Glow peak at 615nm is due to that tester is caused in itself.
Embodiment 6
The glass composition of the present embodiment is SiO2：50mol%；BaO：17mol%；Na2O：20mol%；Al2O3：
5mol%；ZnO：8mol%, and additionally add 1mol% CdS.Frit selects SiO2：Na2CO3、CaCO3、BaCO3、
Al2O3、ZnO、CdS.Each component is weighed by above-mentioned molar percentage, is placed in batch mixer and is well mixed, be placed in after taking-up closed
In corundum crucible, it is then placed in electric furnace and melts 40min at 1350 DEG C, melt is then poured on metal copper mold quick quenching
Shaping, is put into annealing furnace the 2h that annealed at 300 DEG C, obtains pristine glass after furnace cooling, be designated as C6, be cut into specific chi
It is very little, for being heat-treated.
Then pristine glass is placed in heat-treatment furnace, respectively 540-590 DEG C be heat-treated 10h, furnace cooling to room temperature,
CdS quantum dot silicate glass sample is obtained, Absorption and fluorescence spectrum is respectively as shown in Figure 11 and Figure 12.C6-AP is represented
Not thermally treated pristine glass sample, 540 DEG C/10h represents that the rest may be inferred to glass treatment 10h at 540 DEG C.From figure
As can be seen that with the rise of heat treatment temperature, ABSORPTION EDGE is constantly moved to long wave direction.540 DEG C/10h ABSORPTION EDGEs are moved
It is dynamic, illustrate the generation for having quantum dot；Very wide fluorescence peak is observed in fluorescence spectrum, while occurring CdS quantum dot at 500nm
Intrinsic fluorescence peak shoulder.Glow peak in fluorescence spectrum at 690nm is due to that tester is caused in itself.
Embodiment 7
The glass composition of the present embodiment is SiO2：53mol%；CaO：9mol%；BaO：8mol%；Na2O：20mol%；
Al2O3：5mol%；ZnO：5mol%, and additionally add 1mol% CdS.Frit selects SiO2：Na2CO3、CaCO3、
BaCO3、Al2O3、ZnO、CdS.Each component is weighed by above-mentioned molar percentage, is placed in batch mixer and is well mixed, be placed in after taking-up
In closed corundum crucible, it is then placed in electric furnace and melts 40min at 1350 DEG C, be then poured over melt on metal copper mold soon
Fast quenching shaping, is put into annealing furnace the 2h that annealed at 300 DEG C, obtains pristine glass after furnace cooling, be designated as C7, be cut into spy
Fixed size, for being heat-treated.
Then pristine glass is placed in heat-treatment furnace, respectively 540 DEG C, 550 DEG C, 560 DEG C, 570 DEG C, 580 DEG C, 590
DEG C, 610 DEG C of heat treatment 10h, furnace cooling obtains CdS quantum dot silicate glass sample, absorption spectrum and fluorescence light to room temperature
Spectrum difference is as shown in figures 13 and 14.C7-AP represents not thermally treated pristine glass sample, and 540 DEG C/10h is represented at 540 DEG C
Under to glass treatment 10h, the rest may be inferred.It can be seen that with the rise of heat treatment temperature, ABSORPTION EDGE is to long wave direction
It is mobile, illustrate that CdS quantum dot is separated out in glass matrix.The intrinsic glow peak of CdS quantum dot is occurred in that since 540 DEG C/10h
Shoulder (at 450nm), positioned at the defect luminescence that 600nm or so wide in range glow peak is quantum dot.Heat treatment temperature is further raised,
Intrinsic glow peak proportion enhancing, the 570 DEG C/10h intrinsic glow peak of quantum dot (at 476nm) intensity alreadys exceed defect hair
Luminous intensity, because the surface defect of CdS quantum dot is passivated.Temperature is raised, intrinsic glow peak continues to move to long wave direction
It is dynamic, and its intensity enhancing, show obvious fluorescence peak.Glow peak in fluorescence spectrum at 670nm be due to tester in itself
Cause.
Embodiment 8
The glass composition of the present embodiment is SiO2：53mol%；CaO：9mol%；BaO：8mol%；Na2O：20mol%；
Al2O3：3mol%；ZnO：5.5mol%；ZnS：1.5mol%, and additionally add 1mol% CdO.Frit selects SiO2：
Na2CO3、CaCO3、BaCO3、Al2O3、ZnO、ZnS、CdO.Each component is weighed by above-mentioned molar percentage, is placed in batch mixer and mixes
Close uniform, be placed in after taking-up in closed corundum crucible, be then placed in electric furnace and melt 40min at 1350 DEG C, then by melt
Quick quenching shaping is poured on metal copper mold, the 2h that annealed at 300 DEG C is put into annealing furnace, original glass is obtained after furnace cooling
Glass, is designated as C8, is cut into certain size, for being heat-treated.
Then pristine glass is placed in heat-treatment furnace, respectively in 550 DEG C, 570 DEG C, 590 DEG C, 610 DEG C of heat treatment 10h,
Furnace cooling obtains CdS quantum dot silicate glass sample, Absorption and fluorescence spectrum is respectively such as Figure 15 and Figure 16 to room temperature
It is shown.C8-AP represents not thermally treated pristine glass sample, and 550 DEG C/10h is represented at 550 DEG C to glass treatment 10h, according to
This analogizes.It can be seen that with the rise of heat treatment temperature, ABSORPTION EDGE is moved to long wave direction, illustrates CdS quantum dot
Separated out in glass matrix.The intrinsic glow peak shoulder (at 446nm) of CdS quantum dot is occurred in that since 550 DEG C/10h, is located at
550nm or so wide in range glow peak is the defect luminescence of quantum dot.Heat treatment temperature is further raised, intrinsic glow peak institute accounting
Example enhancing, the 570 DEG C/10h intrinsic glow peak of quantum dot (at 494nm) intensity is very nearly the same with defect luminescence intensity, this
It is because the surface defect of CdS quantum dot is passivated.Temperature is raised again, and intrinsic light starts to weaken again, and this is due to too high
Heat treatment temperature, the defect luminescence of glass is higher.Glow peak in fluorescence spectrum at 700nm is due to that tester is made in itself
Into.
Embodiment 9
The glass composition of the present embodiment is SiO2：53mol%；CaO：9mol%；BaO：8mol%；Na2O：20mol%；
Al2O3：5mol%；ZnO：3.5mol%；ZnS：1.5mol%, and additionally add 1mol% CdO.Frit selects SiO2：
Na2CO3、CaCO3、BaCO3、Al2O3、ZnO、ZnS、CdO.Each component is weighed by above-mentioned molar percentage, is placed in batch mixer and mixes
Close uniform, be placed in after taking-up in closed corundum crucible, be then placed in electric furnace and melt 40min at 1350 DEG C, then by melt
Quick quenching shaping is poured on metal copper mold, the 2h that annealed at 300 DEG C is put into annealing furnace, original glass is obtained after furnace cooling
Glass, is designated as C9, is cut into certain size, for being heat-treated.
Then pristine glass is placed in heat-treatment furnace, respectively in 540 DEG C, 550 DEG C, 560 DEG C, 570 DEG C of heat treatment 10h,
Furnace cooling obtains CdS quantum dot silicate glass sample, Absorption and fluorescence spectrum is respectively such as Figure 17 and Figure 18 to room temperature
It is shown.C9-AP represents not thermally treated pristine glass sample, and 540 DEG C/10h is represented at 540 DEG C to glass treatment 10h, according to
This analogizes.It can be seen that with the rise of heat treatment temperature, ABSORPTION EDGE is moved to long wave direction, illustrates CdS quantum dot
Separated out in glass matrix.The intrinsic glow peak shoulder (near 450nm) of CdS quantum dot is occurred in that since 540 DEG C/10h, is located at
550nm or so wide in range glow peak is the defect luminescence of quantum dot.Heat treatment temperature is further raised, intrinsic glow peak institute accounting
Example enhancing, because the surface defect of CdS quantum dot is passivated.570 DEG C are increased the temperature to again, and intrinsic light starts to subtract again
Weak, this is due to too high heat treatment temperature, and the defect luminescence of glass is higher.Glow peak in fluorescence spectrum at 690nm be by
Caused in itself in tester.
Comparative example 1
The glass composition of the present embodiment is SiO2：53mol%；CaO：9mol%；BaO：8mol%；Na2O：20mol%；
Al2O3：5mol%；ZnO：1mol%；ZnS：5mol%, and additionally add 1mol% CdO.Frit selects SiO2：
Na2CO3、CaCO3、BaCO3、Al2O3、ZnO、ZnS、CdO.Each component is weighed by above-mentioned molar percentage, is placed in batch mixer and mixes
Close uniform, be placed in after taking-up in closed corundum crucible, be then placed in electric furnace and melt 40min at 1350 DEG C, then by melt
Quick quenching shaping is poured on metal copper mold, the 2h that annealed at 300 DEG C is put into annealing furnace, original glass is obtained after furnace cooling
Glass, is designated as C11.Because S constituent contents are too high in glass matrix, the complete devitrification of C11 samples.
Claims (8)
1. a kind of CdS quantum dot doped-glass, it is characterised in that described glass basic composition is：SiO2：50~
58mol%；CaO and/or BaO：15-20mol%；Na2O：14~20mol%；Al2O3：3-8mol%；ZnO and/or ZnS：
0.5-11.5mol%, said components sum is 100%；The glass composition also include account for said components sum 0.1~
2.0mol% CdS and/or CdO；Wherein CdS and ZnS total amount constitutes the 4% of component total mole number substantially no more than glass.
2. CdS quantum dot doped-glass as claimed in claim 1, it is characterised in that the CdS quantum dot generated in glass
Fluorescence includes the intrinsic luminous defect luminescence with wide range of quantum dot, and the ratio of intrinsic luminous intensity and defect luminescence intensity
It is adjustable.
3. CdS quantum dot doped-glass as claimed in claim 1, it is characterised in that the introducing of S elements in the glass composition
Mode is ZnS or the incorporation way of CdS, Cd element is CdO or CdS.
4. CdS quantum dot doped-glass as claimed in claim 1, it is characterised in that the molal quantity of sulphur in the glass composition
Higher than the molal quantity of cadmium.
5. the preparation method of CdS quantum dot doped-glass as claimed in claim 1, it is characterised in that the method for glass preparation
It is：Be well mixed after each component by mole being weighed, postforming is melted at high temperature and is annealed；At further heat
Reason prepares CdS quantum dot in glass matrix.
6. the preparation method of CdS quantum dot doped-glass as claimed in claim 5, it is characterised in that CdS quantum dot it is intrinsic
Emission wavelength continuously adjustabe in the range of 400~520nm；CdS quantum dot defect luminescence covers 500~650nm in glass matrix
Scope.
7. the preparation method of CdS quantum dot doped-glass as claimed in claim 5, it is characterised in that the CdS quantum dot is mixed
The composition of miscellaneous glass is：SiO2：50mol%；CaO：9mol%；BaO：8mol%；Na2O：20mol%；Al2O3：5mol%；
ZnO：8mol%, and 1mol% CdS is additionally added, heat treating regime is 530~590 DEG C of processing 10h.
8. the preparation method of CdS quantum dot doped-glass as claimed in claim 5, it is characterised in that the CdS quantum dot is mixed
The composition of miscellaneous glass is：SiO2：53mol%；CaO：9mol%；BaO：8mol%；Na2O：20mol%；Al2O3：5mol%；
ZnO：3.5mol%；ZnS：1.5mol%, and 1mol% CdO is additionally added, heat treating regime is 550~610 DEG C of processing
10h。
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| CN115286252A (en) * | 2022-08-03 | 2022-11-04 | 武汉理工大学 | ZnSe/ZnS core-shell structure quantum dot glass and preparation method thereof |
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| CN104529152A (en) * | 2014-12-17 | 2015-04-22 | 武汉理工大学 | CdSe quantum dot doped glass and preparation method thereof |
| CN104692658A (en) * | 2015-02-27 | 2015-06-10 | 武汉理工大学 | Method for fixing CdS and Se in borosilicate glass |
| CN105293906A (en) * | 2015-12-08 | 2016-02-03 | 武汉理工大学 | CdTe quantum-dot doped glass and preparation method thereof |
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| CN104529152A (en) * | 2014-12-17 | 2015-04-22 | 武汉理工大学 | CdSe quantum dot doped glass and preparation method thereof |
| CN104692658A (en) * | 2015-02-27 | 2015-06-10 | 武汉理工大学 | Method for fixing CdS and Se in borosilicate glass |
| CN105293906A (en) * | 2015-12-08 | 2016-02-03 | 武汉理工大学 | CdTe quantum-dot doped glass and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286252A (en) * | 2022-08-03 | 2022-11-04 | 武汉理工大学 | ZnSe/ZnS core-shell structure quantum dot glass and preparation method thereof |
| CN115286252B (en) * | 2022-08-03 | 2023-09-22 | 武汉理工大学 | ZnSe/ZnS core-shell structure quantum dot glass and preparation method thereof |
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