CN102683369A - Preparation method and application of quantum dot light conversion film for enhancing ultraviolet response of silicon-based imaging device - Google Patents
Preparation method and application of quantum dot light conversion film for enhancing ultraviolet response of silicon-based imaging device Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a quantum dot light conversion film for enhancing ultraviolet response of a silicon-based imaging device. The light conversion film mainly comprises the components of photo conversion luminescent material quantum dots and a film-forming material, wherein the quantum dots are a nano semiconductor material comprising the II-VI or III-V elements in a periodic chart and corresponding nano grains of a core-shell structure; and the film-forming material is one or more of epoxy resin, organosilicon, polyacrylate, polyurethane, ethylene-vinyl acetate copolymer (EVA), polycarbonate (PC) and other polymers. The light conversion film is coated on the surface of a device by adopting flow coating, spray coating, Czochralski, spin coating and other coating processes. According to the invention, the sensitivity of the silicon-based imaging device to ultraviolet light is effectively enhanced, the life of the silicon-based imaging device is prolonged, and the conversion rate from an ultraviolet light area to a visible light area and the optical stability of the film are improved.
Description
Technical field
The present invention relates to a kind of ultraviolet response light conversion film; Be meant a kind of CCD of being applied to (Charge Coupled Device especially; Charge coupled device) or/the ultraviolet response light conversion film of CMOS object surfaces such as (Complementary Metal-Oxide Semiconductor, additional metal oxide semiconductor assemblies).
Background technology
The ultraviolet detection technology is the another dual-use detecting technique that after laser acquisition technology and infrared detection technique, grows up.Current state-of-the-art spectral instrument has mostly adopted CCD or CMOS as sensitive detection parts, and this is to have advantages such as sensitivity is strong, noise is low, good imaging quality because of CCD, CMOS.But because light wave penetration depth in polysilicon of ultraviolet band is very little, generally be lower than 2nm, the ultraviolet band response all very a little less than.This ultraviolet weak response of image device has limited its use in advanced spectral instrument and other field ultraviolet band detections.Since CCD dropped into commodity production with other photo-detector, people just were devoted to seek a kind of method that can improve detector ultraviolet responding ability always.Can find through retrieval; Such as Chinese patent ZL01129954.1 number " ultraviolet camera for criminal investigation ", ZL200820152199.X number " a kind of silica-based image device that strengthens the ultraviolet response based on inorganic material ", ZL200820152099.7 " a kind of silica-based image device ", ZL200810041913.2 number " strengthening the preparation method of ultraviolet response of silicon based image device inorganic thin film ", ZL No. 200810041823.3 " strengthening the organic metal method for manufacturing thin film of ultraviolet response of silicon based image device " etc. with ultraviolet response; All in this problem of discussion; Also all also exist CCD and CMOS a little less than ultraviolet band response very, can't improve sensitivity or the resolution of device in these wave band imagings.
At present, in order to improve detector to ultraviolet sensitiveness, feasible way is by two kinds: a kind of is to increase the ultraviolet response through the silicon substrate structure that changes over the picture device inside; Second kind is that the ultraviolet light that can't respond is converted into visible light, thereby reaches the purpose of imaging at the photosensitive first surfaces coated one deck light conversion film of image device.But organic light conversion film of present stage development has the shortcoming that himself is difficult to overcome, as useful life is short, conversion ratio is not high, excitation spectrum is narrow and emission spectrum is wide and asymmetric, color is non-adjustable, optical stability difference etc.
Summary of the invention
In order to improve the sensitiveness of detector to ultra-violet radiation, the present invention has taked on the photosensitive window of silica-based image device, to be coated with the way of light conversion film, and the information of successfully the ultraviolet band signal source being carried is converted into CCD and the responsive response wave band of CMOS.
Designed a kind of brand-new ultraviolet response light conversion film according to above-mentioned idea this patent, the main component of this light conversion film is photic converting material quantum dot and filmogen.Quantum dot is nanoscale cadmium selenide (CdSe) crystal grain or the cadmium selenide (CdSe) that possesses nucleocapsid structure/zinc sulphide (ZnS) nanocrystal; Filmogen is by in one or more and acetone in epoxy resin, silicone based, polyacrylate, polyurethanes, EVA and the transparent polymer material such as height such as PC grade, toluene, ethanol, chloroform, cyclohexane, the methacrylate equal solvent one or more.The concentration of said quantum dot in filmogen is 0.00001%～30%wt; Using the quantum dot of CdSe/ZnS nucleocapsid structure, is luminous intensity and the stability in order to improve fluorescent material.
The Nano semiconductor micro crystal material is an alleged quantum dot among this paper, is in the semi-conducting material very important one type.Quantum dot typically refers to the Nano semiconductor crystal of particle diameter between 2～8nm, and basic composition material is II-VI family or III-V family element.Because quantum dot has been realized quantum size effect, fluorescence quantum efficiency can be near 100%; Because the size of quantum dot has determined emission wavelength, can obtain the luminescent material of different wave length through the size of the synthetic quantum dot of control, therefore can obtain various colors from same material.Thus; The present invention has not only effectively improved the ultraviolet response of silicon based image device ability; The useful life that has overcome organic light conversion film is short, conversion ratio is not high, excitation spectrum is narrow and the diverging light spectrum width, emission spectrum is wide and asymmetric, shortcomings such as color is non-adjustable, optical stability difference; The susceptibility of silica-based image device be can effectively strengthen, in the life-span of improving silica-based image device, conversion ratio and optical stability improved ultraviolet light.
The preparation process of above-mentioned nanoscale cadmium selenide (CdSe) nucleus:
Step 1 obtains raw material cadmium oxide (CdO), stearic acid (SA) by amount of substance respectively than 1:4, adopts the Schlenk technology, is heated to 150 ℃ after the degassing, the inflation for several times, keeps 25min, and it is colourless that CdO fully is dissolved to, and is cooled to 50 ℃ subsequently;
Step 2, the reaction bulb temperature reduced to 50 ℃ after, the purity that quality such as in there-necked flask, adds greater than 90% three n-octyl phosphine oxides (TOPO) and purity greater than 90% cetylamine (HDA).Adopt the Schlenk technology, drain water and oxygen only through vacuum system after, be heated to 320 ℃ under the ar gas environment.At this moment, use syringe to inject selenium (Se)/tri-n-butyl phosphine (TBP) storing solution fast, and fast cooling to 260 ℃, keep a period of time, withdraw from heater at last, make product be cooled to room temperature;
Step 4; Behind centrifugal the finishing upper solution is outwelled; Add chloroform and acetone mixed liquor (volume ratio 1:3) again and clean solid, centrifugal once more and outwell upper solution, after the pressed powder of remnants be dissolved in promptly obtain nanoscale cadmium selenide (CdSe) nucleus solution in the toluene.
Wherein, said selenium (Se)/tri-n-butyl phosphine (TBP) solution is in the ratio preparation of 1mol/1L.
The preparation process of above-mentioned nanoscale CdSe/ZnS nucleus:
Step 1 is got the toluene solution (10ml) of cadmium selenide (CdSe) nucleus, is expelled in the middle of the mixed solution of three n-octyl phosphine oxides (TOPO) and cetylamine, toluene is extracted out from reaction system under 100 ℃ through the mode that vacuumizes;
Step 2 after the system that step 1 is obtained is warmed up to 200 ℃, successively adds diethyl zinc (ZnEt with the dropping mode
2)/tri-n-butyl phosphine (TBP) solution and sulphur (S)/tri-n-butyl phosphine (TBP) solution, after dropwising, in 200 ℃ of isothermal reactions and stirred 10～50 minutes, after be cooled to room temperature;
Step 4 is outwelled upper solution behind centrifugal the finishing, and adds behind toluene and methyl alcohol mixed liquor (volume ratio 1:3) the cleaning solid centrifugally once more and behind centrifugal finishing, outwell upper solution, remaining solid is dissolved in toluene, cyclohexane or the chloroform preserves at last.
In said step 1, three n-octyl phosphine oxides (TOPO) are 1:1 with the weight ratio of cetylamine (HDA).In said step 2, the reaction system that step 1 obtains and the volume ratio of step 2 dripping quantity are 5:4; Diethyl zinc (ZnEt
2In)/tri-n-butyl phosphine (TBP) solution, diethyl zinc (ZnEt
2) molar concentration be 0.25M; In sulphur (S)/tri-n-butyl phosphine (TBP) solution, the molar concentration of sulphur (S) is 0.25M.
The present invention also provides a kind of membrane preparation method of ultraviolet response light conversion film; Film-forming process such as adopt spin coating, spraying, flow coat and lift applies at device surface and makes; The filmogen that adopts is one or more in epoxy resin, organic silica gel class, esters of acrylic acid, polyurethanes, EVA and the macromolecule such as printing opacity such as height such as PC grade; The agent of epoxy resin gluing is with low polarity epoxide-resin glue, and organic silica gel is used high light transmittance glue, and the acrylate glue class is with low polarity acrylic size; Polyurethane adhesive is with glue classes such as oil soluble polyurethane glue, and optical properties such as EVA and PC preferably resin film.Filmogen and quantum dot adopt hybrid modes such as mechanical agitation, ultrasonic concussion to mix, and coating process is filmed to adopt spin coating, spraying, flow coat then, lift etc.Said film the back in 20 ℃ of-150 ℃ of temperature-curable, curing time 5s-120min, coating thickness is 100nm-5000nm.
Ultraviolet response light conversion film provided by the invention can be applicable to the surface of CCD and cmos device, accepts the low image device surface of ultraviolet light ultraviolet sensitivity degree but reach other.
Description of drawings
Accompanying drawing 1 is the structural representation with silica-based image device of ultraviolet response light conversion film;
Accompanying drawing 2 is absorption spectra illustrated example of ultraviolet response light conversion film provided by the invention;
Accompanying drawing 3 is ultraviolet response light conversion film fluorescence emission spectrum illustrated example.
Embodiment
The present invention provides a kind of and strengthens the silica-based image device that ultraviolet responds based on quantum dot, mainly is not respond ultraviolet light or the more weak problem of response ratio to imageing sensors such as existing C CD, CMOS.Shortcomings such as and the light conversion film that conventional organic coating film method obtains exists phototranstormation efficiency low, and excitation spectrum is narrow, and it is discontinuous to distribute, and emission spectrum is wide and asymmetric, and color is non-adjustable, and optical stability is low and lack useful life.Technical scheme of the present invention is that conversion ratio, optical stability, useful life and the practicality from film taken all factors into consideration, and adopts the quantum dot glue to prepare light conversion film, to improve conversion ratio, practicality and the useful life of photodetector.
The concrete application is embodied in: this light conversion film has the function that changes optical wavelength, the size that can adjust quantum dot in the film and component with the phototransformation of ultraviolet region to the image device specific band of sensitivity; Transmitance between 400-700nm is greater than 85%.But also should have the excitation spectrum wide ranges, emission peak is narrow and symmetrical, the characteristics of color tunable and advantage.The constituent of this light conversion film is A) light conversion material: quantum dot, it comprises periodic table of elements II-VI or III-V same clan nano semiconductor material and corresponding nucleocapsid structure thereof.Specifically comprise with following substance C dSe, CdTe, CdS, ZnSe, ZnS, GaP, GaN, GaAs, InP, InN, InAs, InSb and PbS, PbSe etc. are the quantum dot of nuclear; Or be nuclear with the above-mentioned material, with following substance C dSe, CdS, ZnSe, ZnS, CdO, ZnO, SiO
2Form the nano semiconductor material with nucleocapsid structure Deng for shell, particle diameter is generally less than 10nm.B) filmogen of high transmission rate, it comprises in the macromolecular material of epoxy resin, silicone based, polyacrylate and polyurethanes, EVA and printing opacity such as height such as PC grade one or more.
Designed a kind of ultraviolet response light conversion film according to the problems referred to above, the main component of this film is photic converting material quantum dot and filmogen.Quantum dot is nanoscale cadmium selenide (CdSe) crystal grain or the cadmium selenide (CdSe) that possesses nucleocapsid structure/zinc sulphide (ZnS) nanocrystal; Filmogen is by in the macromolecular material of high transmission rates such as epoxy resin, silicone based, polyacrylate, polyurethanes, EVA and PC one or more.The concentration of said quantum dot in filmogen is 0.00001%～30%wt; Using the quantum dot of CdSe/ZnS nucleocapsid structure, is luminous intensity and the stability in order to have improved fluorescent material.
The preparation process of above-mentioned nanoscale cadmium selenide (CdSe) nucleus:
Step 1 obtains raw material cadmium oxide (CdO), stearic acid (SA) by amount of substance respectively than 1:4, adopts the Schlenk technology, is heated to 150 ℃ after the degassing, the inflation for several times, keeps 25min, and it is colourless that CdO fully is dissolved to, and is cooled to 50 ℃ subsequently;
Step 2, the reaction bulb temperature reduced to 50 ℃ after, the purity that quality such as in there-necked flask, adds greater than 90% three n-octyl phosphine oxides (TOPO) and purity greater than 90% cetylamine (HDA).Adopt the Schlenk technology, drain water and oxygen only through vacuum system after, be heated to 320 ℃ under the ar gas environment.At this moment, use syringe to inject selenium (Se)/tri-n-butyl phosphine (TBP) storing solution fast, and fast cooling to 260 ℃, keep a period of time, withdraw from heater at last, make product be cooled to room temperature;
Step 4; Behind centrifugal the finishing upper solution is outwelled; Add chloroform and acetone mixed liquor (volume ratio 1:3) again and clean solid, centrifugal once more and outwell upper solution, after the pressed powder of remnants be dissolved in promptly obtain nanoscale cadmium selenide (CdSe) nucleus solution in the toluene.
Wherein, said selenium (Se)/tri-n-butyl phosphine (TBP) solution is in the ratio preparation of 1mol/1L.
The preparation process of above-mentioned nanoscale CdSe/ZnS nucleus:
Step 1 is got the toluene solution (10ml) of cadmium selenide (CdSe) nucleus, is expelled in the middle of the mixed solution of three n-octyl phosphine oxides (TOPO) and cetylamine, toluene is extracted out from reaction system under 100 ℃ through the mode that vacuumizes;
Step 2 after the system that step 1 is obtained is warmed up to 200 ℃, successively adds diethyl zinc (ZnEt with the dropping mode
2)/tri-n-butyl phosphine (TBP) solution and sulphur (S)/tri-n-butyl phosphine (TBP) solution, after dropwising, in 200 ℃ of isothermal reactions and stirred 10～50 minutes, after be cooled to room temperature;
Step 4 is outwelled upper solution behind centrifugal the finishing, and adds behind toluene and methyl alcohol mixed liquor (volume ratio 1:3) the cleaning solid centrifugally once more and behind centrifugal finishing, outwell upper solution, remaining solid is dissolved in toluene, cyclohexane or the chloroform preserves at last.
In said step 1, three n-octyl phosphine oxides (TOPO) are 1:1 with the weight ratio of cetylamine (HDA).In said step 2, the reaction system that step 1 obtains and the volume ratio of step 2 dripping quantity are 5:4; Diethyl zinc (ZnEt
2In)/tri-n-butyl phosphine (TBP) solution, diethyl zinc (ZnEt
2) molar concentration be 0.25M; In sulphur (S)/tri-n-butyl phosphine (TBP) solution, the molar concentration of sulphur (S) is 0.25M.
The present invention also provides a kind of ultraviolet response light conversion film preparation method; Film-forming process such as adopt spin coating, spraying, flow coat, lift applies at device surface and makes; The filmogen that adopts is one or more of high light transmittance macromolecular materials such as epoxy resin, organic silica gel class, polyacrylate, polyurethanes, EVA and PC; The agent of epoxy resin gluing is with low polarity epoxide-resin glue; Organic silica gel is used high light transmittance glue, and the acrylate glue class is with low polarity acrylic size, and polyurethane adhesive is filmed with oil soluble polyurethane glue.Filmogen and quantum dot adopt hybrid modes such as mechanical agitation, ultrasonic concussion to mix, and coating process is filmed to adopt spin coating, spraying, flow coat then, lift etc.Said back photocuring or 20 ℃ of-150 ℃ of temperature-curable under uviol lamp of filming, curing time 5s-120min, coating thickness is 100nm-5000nm.
Compare existing organic light conversion film, ultraviolet response quantum dot light conversion film provided by the invention (following abbreviation quantum dot film) has higher transformation efficiency, exciting light spectrum width and continuous distribution; And emission spectrum is narrow and symmetrical, color tunable, and photochemical stability is high; Superior fluorescent characteristics such as fluorescence lifetime is long; And technology is simple, makes things convenient for large-scale production, so the quantum dot film has unique significance because in this field.Simultaneously; With nanocrystalline as a kind of novel fluorescence converting material; Light conversion film is made on the surface that is coated onto silica-based image device; The information with ultraviolet band that can success be transformed into the responsive response wave band of CCD and CMOS, and because of the high light transmittance of its light conversion film, can guarantee simultaneously that CCD and CMOS can not lose original resolution.
Can find that from spectrogram 2 light below the 600nm wavelength all just can be absorbed by the quantum dot light conversion film.Can know that from emission spectrum Fig. 3 made light conversion film is after having absorbed high-octane light source, the emitting fluorescence scope is between 570nm-620nm, and emission peak is at the 590nm place.This this film of explanation can be transformed into the light signal of low band the high band light that can be responded to by image device, thereby realizes the ultraviolet response of photoelectric device.Therefore quantum dot ultraviolet response light conversion film of the present invention is a kind of wide exciting, the film of narrow emission.
Embodiment 1
The preparation process of nanoscale cadmium selenide (CdSe) nucleus:
Step 1 obtains raw material cadmium oxide (CdO), stearic acid (SA) by amount of substance respectively than 1:4, adopts the Schlenk technology, is heated to 150 ℃ after the degassing, the inflation for several times, keeps 25min, and it is colourless that CdO fully is dissolved to, and is cooled to 50 ℃ subsequently;
Step 2, the reaction bulb temperature reduced to 50 ℃ after, the purity that quality such as in there-necked flask, adds greater than 90% three n-octyl phosphine oxides (TOPO) and purity greater than 90% cetylamine (HDA).Adopt the Schlenk technology, drain water and oxygen only through vacuum system after, it is heated to 320 ℃.Use syringe to inject selenium (Se)/tri-n-butyl phosphine (TBP) storing solution, and fast cooling to 260 ℃, keep a period of time, withdraw from heater at last, make product be cooled to room temperature;
Step 4; Behind centrifugal the finishing upper solution is outwelled; Add chloroform and acetone mixed liquor (volume ratio 1:3) solution again and clean solid, centrifugal once more and outwell upper solution, after the pressed powder of remnants be dissolved in promptly obtain nanoscale cadmium selenide (CdSe) nucleus solution finished product in the toluene.
Wherein, said selenium (Se)/tri-n-butyl phosphine (TBP) solution is in the ratio preparation of 1mol/1L.
Embodiment 2
Preparation process with quantum dot of CdSe/ZnS nucleocapsid structure:
Step 1 is got the toluene solution (10ml) of cadmium selenide (CdSe) nucleus, is expelled in the middle of the mixed solution of three n-octyl phosphine oxides (TOPO) and cetylamine, toluene is extracted out from reaction system under 100 ℃ through the mode that vacuumizes;
Step 2 after the system that step 1 is obtained is warmed up to 200 ℃, successively adds diethyl zinc (ZnEt with the dropping mode
2)/tri-n-butyl phosphine (TBP) solution and sulphur (S)/tri-n-butyl phosphine (TBP) solution, after dropwising, in 200 ℃ of isothermal reactions and stirred 10～50 minutes, after be cooled to room temperature;
Step 4 is outwelled upper solution behind centrifugal the finishing, and adds behind toluene and methyl alcohol mixed liquor (volume ratio 1:3) the cleaning solid centrifugally once more and behind centrifugal finishing, outwell upper solution, remaining solid is dissolved in toluene, cyclohexane or the chloroform preserves at last.
In said step 1, three n-octyl phosphine oxides (TOPO) are 1:1 with the weight ratio of cetylamine (HDA).In said step 2, the reaction system that step 1 obtains and the volume ratio of step 2 dripping quantity are 5:4; Diethyl zinc (ZnEt
2In)/tri-n-butyl phosphine (TBP) solution, diethyl zinc (ZnEt
2) molar concentration be 0.25M; In sulphur (S)/tri-n-butyl phosphine (TBP) solution, the molar concentration of sulphur (S) is 0.25M.
The silica-based image device of quantum dot epoxy jelly membrane
A. at first a certain amount of quantum dot is dissolved in the toluene solvant, processes 5% toluene solution;
B. weighing 4g epoxy glue adds an amount of quantum dot solution in epoxy glue, and making the concentration of quantum dot in mixed liquor is 2%, and mixes;
C. the photosensitive first substrate with cleaned silica-based image device is positioned in the spin coating appearance;
D. regulate spin coating appearance rotating speed at 1500 commentaries on classics/min, rotational time 45 seconds;
E. the quantum dot solution for preparing is evenly dripped on photosensitive first substrate of silica-based image device, spin coating finishes the back and forms micron-sized film;
F.100 ℃ heating 1h after the solvent evaporates that contains in the coated film, just forms the quantum dot light conversion film of ultraviolet response.
Embodiment 4
The silica-based image device of quantum dot polyacrylate glued membrane
A. at first a certain amount of quantum dot is dissolved in butyl methacrylate and azo-bis-isobutyl cyanide (1%wt) solvent, processes 10% butyl methacrylate quantum dot solution;
B. the photosensitive first substrate with cleaned silica-based image device is positioned in the spin coating appearance;
C. regulate spin coating appearance rotating speed at 1000 commentaries on classics/min, rotational time 30 seconds;
D. the quantum dot solution for preparing is evenly dripped on photosensitive first substrate of silica-based image device, spin coating finishes the back and forms micron-sized film;
E.150 ℃ heating 30min just forms the quantum dot change light conversion film that ultraviolet responds.
Embodiment 5
The silica-based image device of quantum dot organosilicon glued membrane
A. at first a certain amount of quantum dot is dissolved in the n-hexane solvent, processes 10% n-hexane quantum dot solution;
B. weighing 6g organic silica gel adds an amount of quantum dot solution in organic silica gel, and making the concentration of quantum dot in mixed liquor is 2%, and mixes;
C. the photosensitive first substrate with cleaned silica-based image device is positioned in the spin coating appearance;
D. regulate spin coating appearance rotating speed at 1400 commentaries on classics/min, rotational time 45 seconds;
E. the quantum dot solution for preparing is evenly dripped on photosensitive first substrate of silica-based image device, spin coating finishes the back and forms micron-sized film;
F.140 ℃ heating 40min just forms the quantum dot light conversion film that ultraviolet responds.
Embodiment 6
The silica-based image device of quantum dot polyurethane adhesive
A. at first a certain amount of quantum dot is dissolved in the vinyl acetate ester solvent, processes 8% vinylacetate quantum dot solution;
B. weighing 6g polyurethane adhesive adds an amount of quantum dot solution in polyurethane adhesive, and making the concentration of quantum dot in mixed liquor is 2%, and mixes;
C. the photosensitive first substrate with cleaned silica-based image device is positioned in the spin coating appearance;
D. regulate spin coating appearance rotating speed at 1200 commentaries on classics/min, rotational time 50 seconds;
E. the quantum dot solution for preparing is evenly dripped on photosensitive first substrate of silica-based image device, spin coating finishes the back and forms micron-sized film;
F.60 ℃ heating 2h just forms the quantum dot light conversion film that ultraviolet responds.
Claims (9)
1. one kind is used to strengthen the quantum dot light conversion film of silica-based image device to the ultraviolet response; It is characterized in that: form light conversion film by the filmogen of quantum dot and high transmission rate with change optical wavelength function; This film can be with the phototransformation of ultraviolet region to the most responsive specific band of image device, and to make optical wavelength be that the transmitance of the light between 400nm～700nm is greater than 85%.
2. quantum dot light conversion film according to claim 1 is characterized in that: said quantum dot comprises periodic table of elements II-VI or III-V same clan nano semiconductor material and corresponding nucleocapsid structure thereof; Specifically comprise with following substance C dSe, CdTe, CdS, ZnSe, ZnS, GaP, GaN, GaAs, InP, InN, InAs, InSb, PbS and PbSe etc. are the quantum dot of nuclear; Or be nuclear with the above-mentioned material, with following substance C dSe, CdS, ZnSe, ZnS, CdO, ZnO and SiO
2Form the nano semiconductor material with nucleocapsid structure Deng for shell, particle diameter is less than 10nm; The filmogen of described high transmission rate comprises one or more in epoxy resin, silicone based, polyacrylate, polyurethanes, EVA and the light transmissive material such as height such as PC grade.
3. quantum dot light conversion film according to claim 1 and 2; It is characterized in that: said quantum dot is cadmium selenide (CdSe) nanocrystal; Or be the nanocrystal of nanoscale CdSe/ZnS nucleocapsid structure, its concentration in filmogen is 0.00001～30%wt.
4. quantum dot light conversion film according to claim 3 is characterized in that: the preparation process of said nanoscale cadmium selenide (CdSe) nucleus:
Step 1 obtains raw material cadmium oxide (CdO), stearic acid (SA) by amount of substance respectively than 1:4, adopts the Schlenk technology, is heated to 150 ℃ after the degassing, the inflation for several times, keeps 25min, and it is colourless that CdO fully is dissolved to, and is cooled to 50 ℃ subsequently;
Step 2, the reaction bulb temperature reduced to 50 ℃ after, the purity that quality such as in there-necked flask, adds greater than 90% three n-octyl phosphine oxides (TOPO) and purity greater than 90% cetylamine (HDA); Adopt the Schlenk technology, drain water and oxygen only through vacuum system after, be heated to 320 ℃ under the ar gas environment; At this moment, use syringe to inject selenium (Se)/tri-n-butyl phosphine (TBP) storing solution fast, and fast cooling to 260 ℃, keep a period of time, withdraw from heater at last, make product be cooled to room temperature;
Step 3 adds isopyknic chemical pure chloroform in the liquid that the step 2 of reducing to room temperature obtains, add the chemical pure acetone of 3 times of volumes again after, will have solid to separate out, treat that solid separates out deposition and finish, centrifugal 1～10 minute with 3000～5000rpm;
Step 4; Behind centrifugal the finishing upper solution is outwelled; Add chloroform and acetone mixed liquor (volume ratio 1:3) again and clean solid, centrifugal once more and outwell upper solution, after the pressed powder of remnants be dissolved in promptly obtain nanoscale cadmium selenide (CdSe) nucleus solution in the toluene.
5. quantum dot light conversion film according to claim 3 is characterized in that: the preparation process of said nanoscale CdSe/ZnS nucleus does,
Step 1 is got the toluene solution (10ml) of cadmium selenide (CdSe) nucleus, be expelled in the middle of the mixed solution of three n-octyl phosphine oxides (TOPO) and cetylamine, through the mode that vacuumizes 100
oUnder the C toluene is extracted out from reaction system;
Step 2, the system that step 1 is obtained is warmed up to 200
oBehind the C, successively add diethyl zinc (ZnEt with the dropping mode
2)/tri-n-butyl phosphine (TBP) solution and sulphur (S)/tri-n-butyl phosphine (TBP) solution is after dropwising, in 200
oC isothermal reaction and stirring simultaneously 10～50 minutes, after be cooled to room temperature;
Step 3 at room temperature adds chemical pure methyl alcohol in the solution that step 2 obtains, treat that solid is separated out post precipitation in the solution, at 3000～5000rpm centrifugal 1～10 minute;
Step 4 is outwelled upper solution behind centrifugal the finishing, and adds behind toluene and methyl alcohol mixed liquor (volume ratio 1:3) the cleaning solid centrifugally once more and behind centrifugal finishing, outwell upper solution, remaining solid is dissolved in toluene, cyclohexane or the chloroform preserves at last.
6. quantum dot light conversion film according to claim 5 is characterized in that: in the said step 1, three n-octyl phosphine oxides (TOPO) are 1:1 with the weight ratio of cetylamine (HDA); In the said step 2, the reaction system that step 1 obtains and the volume ratio of step 2 dripping quantity are 5:4; Diethyl zinc (ZnEt
2In)/tri-n-butyl phosphine (TBP) solution, diethyl zinc (ZnEt
2) molar concentration be 0.25M; In sulphur (S)/tri-n-butyl phosphine (TBP) solution, the molar concentration of sulphur (S) is 0.25M.
7. according to the film build method of each described quantum dot light conversion film in the claim 1 to 6; It is characterized in that: coating process such as described quantum dot light conversion film adopts spin coating, spraying, flow coat, lift apply at device surface and make; The filmogen that adopts is optical properties such as epoxy resin, organic silica gel class, esters of acrylic acid, polyurethanes glue, EVA and PC one or more in the macromolecular material preferably; The agent of epoxy resin gluing is with low polarity epoxide-resin glue; Organic silica gel is used high light transmittance glue, and the acrylate glue class is with low polarity acrylic size, and polyurethane adhesive is filmed with oil soluble polyurethane glue; Filmogen and quantum dot adopt hybrid modes such as mechanical agitation, ultrasonic concussion to mix, and coating process is filmed to adopt spin coating, spraying, flow coat then, lift etc.
8. the film build method of quantum dot light conversion film according to claim 7 is characterized in that, the back of filming is in 20 ℃ of-150 ℃ of temperature-curable, perhaps photocuring, curing time 5s-120min, coating thickness is 100nm-5000nm.
9. can use on the surface of silica-based image devices such as CCD and CMOS according to the quantum dot light conversion film that claim 7 obtained, or on other surfaces, use the insensitive image device of ultraviolet light.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN103745981A (en) * | 2013-12-04 | 2014-04-23 | 广东普加福光电科技有限公司 | Ultraviolet response type rare earth light conversion film and application thereof |
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| CN109233818A (en) * | 2017-07-11 | 2019-01-18 | 北京师范大学 | Mn doping ZnS superfine nanowire of selective absorbing day-old chick ultraviolet light and its preparation method and application |
| CN109935608A (en) * | 2019-03-04 | 2019-06-25 | 东南大学 | A kind of day blind ultraviolet detection structure and preparation method thereof introducing quantum dot |
| CN111349431A (en) * | 2020-02-25 | 2020-06-30 | 纳晶科技股份有限公司 | Core-shell quantum dots and photovoltaic devices |
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| CN103901003A (en) * | 2012-12-28 | 2014-07-02 | 华东理工大学 | Method for detecting and monitoring cracks of mechanical parts by utilizing fluorescent quantum dots |
| CN103745981A (en) * | 2013-12-04 | 2014-04-23 | 广东普加福光电科技有限公司 | Ultraviolet response type rare earth light conversion film and application thereof |
| CN103709731A (en) * | 2013-12-27 | 2014-04-09 | Tcl集团股份有限公司 | Quantum dot/polyurethane nano crystal complex and preparation method thereof as well as colorful conversion film |
| CN106574176A (en) * | 2014-08-04 | 2017-04-19 | 罗地亚经营管理公司 | Modified phosphors and compositions thereof |
| CN106206636A (en) * | 2016-08-16 | 2016-12-07 | 京东方科技集团股份有限公司 | A kind of X-ray detection panel and preparation method thereof |
| CN106811191A (en) * | 2016-12-27 | 2017-06-09 | 广东阿格蕾雅光电材料有限公司 | The light conversion film of the green glow dyestuff containing aggregation-induced emission property |
| CN109233818A (en) * | 2017-07-11 | 2019-01-18 | 北京师范大学 | Mn doping ZnS superfine nanowire of selective absorbing day-old chick ultraviolet light and its preparation method and application |
| CN108123008A (en) * | 2017-12-04 | 2018-06-05 | 东南大学 | A kind of ultraviolet detection system and method based on doped quantum dot wavelength convert |
| CN113423789A (en) * | 2018-12-06 | 2021-09-21 | 科迪华公司 | Stabilized printing material |
| US11945961B2 (en) | 2018-12-06 | 2024-04-02 | Kateeva, Inc. | Stabilized print materials |
| CN109935608A (en) * | 2019-03-04 | 2019-06-25 | 东南大学 | A kind of day blind ultraviolet detection structure and preparation method thereof introducing quantum dot |
| CN111349431A (en) * | 2020-02-25 | 2020-06-30 | 纳晶科技股份有限公司 | Core-shell quantum dots and photovoltaic devices |
| CN111349431B (en) * | 2020-02-25 | 2024-02-09 | 纳晶科技股份有限公司 | Core-shell quantum dot and photoelectric device |
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