CN110126257A - A kind of 3D printing method of intensity controlled semiconductor nano flexible photoelectric device - Google Patents
A kind of 3D printing method of intensity controlled semiconductor nano flexible photoelectric device Download PDFInfo
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- CN110126257A CN110126257A CN201910401853.9A CN201910401853A CN110126257A CN 110126257 A CN110126257 A CN 110126257A CN 201910401853 A CN201910401853 A CN 201910401853A CN 110126257 A CN110126257 A CN 110126257A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- H—ELECTRICITY
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
- H01L31/1832—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe comprising ternary compounds, e.g. Hg Cd Te
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention relates to a kind of 3D printing methods of intensity controlled semiconductor nano flexible photoelectric device, belong to fluorescence aggregation, fluorescence imaging, photodetection field.A kind of 3D printing method of intensity controlled semiconductor nano flexible photoelectric device of the invention, 3D printing technique molding is carried out by the way that semiconductor nano solution and flexible matrix to be sufficiently mixed, the flexible matrix semiconductor nano device that available traditional technology is difficult to realize, and the anisotropy device that available traditional technology is difficult to realize, it can with qualitative, quantitative control the power of certain point or the photoelectric properties of certain one side, substantially increase the performance of semiconductor nano device, and it can largely be saved material by way of increasing material manufacturing, device performance is ensured that using a small amount of semiconductor nano, save material and efficiently.
Description
Technical field
The present invention relates to a kind of 3D printing methods of intensity controlled semiconductor nano flexible photoelectric device, and it is poly- to belong to fluorescence
Collection, fluorescence imaging, photodetection field.
Background technique
Nanocrystalline colloidal semiconductor is a kind of inorganic functional material synthesized in the solution, because what size, pattern generated
Quantum size, confinement effect etc. have unique Wuli-Shili-Renli system approach and optics abundant, electric property.Its surface is covered with
One layer of long-chain organic ligand protective layer, making it in organic solvent has good dispersibility, while such material is had
The characteristic of large area solution processing.This kind of nanocrystalline material is in bio-imaging, light emitting diode, laser and solar battery etc.
Aspect has obtained extensive research, shows huge application potential.However, the practical application nanocrystalline in colloidal semiconductor
In, the device technology of macro-size has its photoelectric properties important influence.Currently, semiconductor photoelectric device mostly uses
Traditional manufacturing method forms the device of specific shape by existing mold and fixture, but its difficulty of processing is larger, and
The device shape and size of formation are difficult to realize Effective Regulation.Especially for the flexible semiconductor photoelectric device of labyrinth
Synthesis, traditional handicraft are difficult to realize its controllable preparation.In addition, traditional handicraft also has very greatly the photoelectric properties of colloid nanocrystalline
It influences.By taking colloidal semiconductor quantum dot as an example, traditional handicraft can be such that quantum dot closely connects, or even reunite, this amount of directly resulting in
The quantum yield and exciton lifetime of son point are greatly reduced.Therefore, the system of the photoelectric device of the labyrinth of universality how is realized
It is standby, and guarantee the photoelectric properties of colloid nanocrystalline to greatest extent, it is of great significance.
3D printing technique, i.e. increases material manufacturing technology are a kind of to form 3D solid by successively increasing accumulation material
Quick increases material manufacturing technology has compared with tradition subtracts material manufacturing technology and is lost that low, product manufacturing is diversified, precision and height
The characteristics of effect, particularly with regard to complicated shape and high-end manufacturing field, 3D printing technique is shown different from conventionally manufactured
The huge superiority of technology.Retrofit may be implemented with the comparable process control of optical dimensions, prepare answering for micro-nano-scale
Miscellaneous structure, the research and application for photoelectric properties are significant.Therefore, how by this advanced micro-nano of 3D printing across ruler
Manufacturing technology is spent in conjunction with the semiconductor nano material with photoelectric properties, it is soft using environmental-friendly polylactic acid, silica gel etc.
Property matrix realize 3 D complex structure preparation while, to greatest extent keep colloid nanocrystalline because nano effect generate it is rich
Rich photoelectric properties with important science and apply valence for complicated photoelectric device, the especially preparation of flexible matrix device
Value.
3D printing technique is applied in the printing of semiconductor nano material macroscopic view, nanocrystalline height point on the one hand can be made
It dissipates in flexible matrix, improves nanocrystalline utilization efficiency；On the other hand it can be controlled by constructing specific structure
Device can have different performances in a different direction.Many is obtained with using nanocrystalline on a small quantity using this technology
Photovoltaic applications abundant.
Summary of the invention
It shines uncontrollable the purpose of the present invention is to solve existing semiconductor nano flexible photoelectric device, is unable to satisfy
The problem of use demand, provides a kind of 3D printing method of intensity controlled semiconductor nano flexible photoelectric device.This method benefit
The characteristics of being different from the retrofit that traditional processing means are difficult to realize with 3D printing constructs specific structural approach, realization pair
Device performance it is controllable, to cope with, semiconductor nano device fabrication difficulty is larger in existing preparation method, is not easy to industrialize
Production, and formed device shape and standard shape between have differences, etc. technical problems.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of 3D printing method of intensity controlled semiconductor nano flexible photoelectric device, comprising the following steps:
(1) preparation of semiconductor nano: the semiconductor nano in this method includes the size of liquid phase reactor preparation, shape
The monodispersed quantum dot of looks, doped quantum dot, heterojunction structure (metal/semiconductor nucleocapsid, heterodimer structure) are nanocrystalline etc.,
It is prepared, and can be distributed to by regulating and controlling surface ligand using hot injection method or low temperature cationic exchange process
In different solvents；
(2) 3D printing slurry preparation: chloroform, the nothings such as the organic solvents such as toluene or water are dispersed by semiconductor nano
Semiconductor nanocrystalline sol is obtained in solvent, this colloidal sol is uniformly mixed with the flexible matrix with certain rheological properties matter, is obtained
To 3D printing slurry；
(3) 3D printing flexible matrix semiconductor nano device: by direct write 3D printing technique (3D model is established, is arranged
Jet diameters print distance, the parameters such as print speed) three-dimensional structure molding is carried out to obtained slurry, it forms semiconductor and receives
The brilliant device semi-finished product of rice, design different path angles according to different needs, may be implemented to specified point, performance in certain surface
Control, structural anisotropy's device.
(4) flexible matrix semiconductor nano device solidifies: the semiconductor nano device semi-finished product are dried,
So that it is formed by curing stable semiconductor nano device.
In step (1), the semiconductor nano can be nanocrystalline for any colloidal semiconductor, mainly includes doping
Son point and hetero-nanocrystals, the Ag of preferably liquid phase method preparation adulterate CdS, and Cu adulterates CdS, and Ag adulterates CdSe, and Cu adulterates CdSe,
Ag adulterates ZnS, and Cu adulterates ZnS, Au-HgxCd1-xTe core-shell nano is brilliant, and Au-CdS core-shell nano is brilliant, and synthetic method can adopt
It is prepared with any existing method.
Specific preparation step:
In step (2), preparing 3D printing slurry includes carrying out surface ligand processing, dissolution to the semiconductor nano of preparation
Semiconductor nano solution is obtained in chloroform, the organic solvents such as toluene or in the inorganic solvents such as water, solution and 3D printing is former
Uniformly mixing can make semiconductor nano fully dispersed to material, obtain 3D printing slurry.
Particularly, the nanocrystalline device of flexible semiconductor that can be made by adding curing agent is able to maintain that stable shape
Shape, the curing agent of addition and the mass ratio of flexible matrix are not more than 10%
Particularly, the semiconductor nano concentration in the semiconductor nanocrystalline sol is 10wt% to 99wt%；It is described
Semiconductor nanocrystalline sol and the mass ratio of flexible matrix are not more than 10%；
In step (3), about jet diameters: jet diameters are bigger, and it is easier to discharge, and the lines of printing are thicker, printing essence
Exactness is lower；Jet diameters are smaller, and discharging lines are thinner, and the surface of printing objects is more smooth, and accuracy is higher.Jet diameters
It may range from 0.01~0.5mm printing precision according to actual needs, choose the spray head of corresponding size.
In step (3), about printing distance: height of the printing head apart from print platform can significantly affect the accurate of printing
Property.Excessively high printing distance will lead to extrusion lines cannot complete and print platform and the lines extruded stick one
Rise, occur printing dislocation phenomena such as, printing apart from it is too low when can make again spray head extruding or scrape printed object, together
Sample reduces printing precision.Jet diameters are 0.01~0.5mm, and print platform and nozzle distance can choose 0.02~0.4mm.Example
Such as, under the conditions of jet diameters 0.2mm, print platform height and nozzle distance can choose 0.16mm.
In step (3), about print speed: print speed is too fast, and the material of extrusion has little time to stick in material before
Together, it will lead to bridging phenomenon；Print speed is excessively slow to make the material squeezed out crimp again, influence printing precision.
Print speed is between 5~20mm/s, such as 10mm/s, and the lines printed are more uniform and can maintain its original shape.
In step (3), about printing path: according to different requirements, can by designing different printing path, or
It constructs different printing angle and realizes that device, and the angle of printing path is got in the quantitative enhancing of certain point or certain one side
Small, reinforcing effect is more obvious, to realize the regulation to performance.
In step (4), flexible matrix semiconductor nano is solidified, air drying, baking oven heating, drying can be used
Etc. modes to semiconductor nano device after molding carry out curing process.
Beneficial effect
The 3D printing method of a kind of intensity controlled semiconductor nano flexible photoelectric device of the invention, by by semiconductor
Nanocrystal solution and flexible matrix, which are sufficiently mixed, carries out 3D printing technique molding, the flexibility that available traditional technology is difficult to realize
Matrix semiconductor nano device, and the anisotropy device that available traditional technology is difficult to realize, can be with qualitative, quantitative
Ground controls the power of certain point or the photoelectric properties of certain one side, substantially increases the performance of semiconductor nano device, and lead to
The mode for crossing increasing material manufacturing can largely save material, and ensure that device performance using a small amount of semiconductor nano,
Save material and efficiently.
Detailed description of the invention
Fig. 1 is to enhance device pictorial diagram and fluorescence by the molding equilateral triangle controllable fluorescent of the 3D printing of matrix of polylactic acid
Strength test figure；Wherein, figure a is that controllable fluorescent enhances device pictorial diagram；Scheming b is the fluorescence intensity survey that controllable fluorescent enhances device
Attempt；It can be seen that the fluorescence intensity in angle is higher than side edge in a figure, the angle as the result is shown of the quantitative test in b figure
Fluorescence intensity be 7 times of fluorescence intensity of side edge.
Fig. 2 is the polygon fluorescent device printed using polylactic acid and silica gel as matrix；Wherein, figure a is using polylactic acid as base
The polygon fluorescent device figure of matter；Scheming b is using silica gel as the polygon fluorescent device figure of matrix；
Fig. 3 is that the molding edge orientation of 3D printing for being 25% as the semiconductor nano mass fraction of matrix using silica gel prints
Controllable fluorescent enhancing device pictorial diagram and fluorescence intensity test chart；Wherein, figure a is the pictorial diagram that controllable fluorescent enhances device；
Scheming b is the fluorescence intensity test chart that controllable fluorescent enhances device；Quantitative test in b figure is as the result is shown perpendicular on Print direction
Fluorescence intensity be 2 times of fluorescence intensity for being parallel to Print direction.
Fig. 4 is that the molding edge orientation of 3D printing for being 50% as the semiconductor nano mass fraction of matrix using silica gel prints
Controllable fluorescent enhancing device pictorial diagram and fluorescence intensity test chart；Wherein, figure a is the pictorial diagram that controllable fluorescent enhances device；
Scheming b is the fluorescence intensity test chart that controllable fluorescent enhances device；Quantitative test in b figure is as the result is shown perpendicular on Print direction
Fluorescence intensity be 2 times of fluorescence intensity for being parallel to Print direction.
Fig. 5 is using polylactic acid as the concentric loop device of the printing of matrix, and figure a and figure b are different viewing angles, as a result
The fluorescence intensity observed in display different angle has very big difference.
Specific embodiment
The content of present invention is further illustrated combined with specific embodiments below, but should not be construed as limiting the invention.If
Conventional means not specified, that technological means used in embodiment is well known to those skilled in the art, except non-specifically saying
Bright, reagent of the present invention, method and apparatus are the art conventional reagent, method and apparatus.
Embodiment 1
The present embodiment prepares flexible matrix semiconductor nano device by taking doped quantum dot CdS:Ag as an example.
A kind of 3D printing method of intensity controlled semiconductor nano flexible photoelectric device, the specific steps are as follows:
The preparation of semiconductor nano: the toluene colloidal sol of Ag is prepared first: by 20mL oleic acid, 20mL oleyl amine and 0.34g
AgNO3It is added in flask, 5min is stirred at 30 DEG C, 0.08g Fe (NO is added later3)3·4H2O raises the temperature to 120 DEG C,
It is gradually warmed up stirring, the reaction was continued when being warming up to 120 DEG C 1h, addition volume ratio is 1:3 ethyl alcohol, is centrifuged later with 5000rpm
8min after sucking supernatant, precipitating obtained by bottom is dispersed in 14mL toluene, the toluene colloidal sol of 4nm Ag is obtained.
Then it prepares sulphur precursor solution: 10m1 oleyl amine, 20mL oleic acid and 128mg sulphur powder being placed in flask, in room
The lower stirring of temperature is stirred to react 40min at 100 DEG C, is added 30m1 toluene thereto, it is to be mixed uniformly after, it is molten to obtain sulphur presoma
Liquid.
Ag2The preparation of S nano particle colloidal sol: the toluene colloidal sol of the monodispersed 5nm Ag of 350 μ L is taken to burn in the round bottom of 25mL
In bottle, 6m1 toluene and 3mL sulphur precursor solution are added thereto, reacts 1h in 50 DEG C of stirred in water bath, appropriate second is added
Alcohol obtains monodispersed Ag with 6000rpm centrifuge washing 10min2S nano particle.It distributes it in 6-10m1 toluene, obtains
To Ag2The toluene colloidal sol of S nano particle.
The CdS of Ag doping nanocrystalline preparation: by monodispersed Ag obtained above2S nano particle colloidal sol, is being stirred
Under, 0.2mL oleic acid, 0.1mL oleyl amine and suitable Cd (NO is added3)2·4H2O methanol solution (0.1g/m1), magnetic force stirs at room temperature
3min is mixed, 0.1mLTBP is added, reacts 2h in 60 DEG C of stirred in water bath, ethyl alcohol is added and is obtained with 5000rpm centrifuge washing 8min
Obtain CdS:Ag doped quantum dot.
Print slurry configuration: in 50 DEG C of water-baths under heating state, the high-purity C dS:Ag doped quantum dot of preparation is molten
In 1mL chloroform, 5g polylactic acid is added, adding 5mL chloroform is uniformly mixed polylactic acid dissolution with doped quantum dot, and holds
Continuous stirring, until system occurs thick, whens flow difficulties, stops heating, and taking-up obtains 3D printing slurry.
3D printing molding: the slurry of preparation is put into printer charging basket, is chosen the printing head that diameter is 0.2mm, is used
Computer manufacture 3D model, and carry out the parameter setting, print speed 10mm/s such as being sliced, print temperature is 25 DEG C, and printing is flat
Platform height is 0.18mm, carries out 3D printing, obtains flexible matrix semiconductor nano devices semi-finished product.
In the present embodiment, as equilateral triangle, the structure of 60 ° of angle of construction is successively printed, is obtained the printing path set
Hollow triangular-prism structure as shown in Figure 1a, reaches the enhancing to fluorescence intensity at incline.
Semi-finished product solidification: the present embodiment is using polylactic acid printed material, and drying at room temperature is stood after printing
Curing molding, as shown in Figure 1a, obtained flexible device have apparent fluorescence congregational rate, detect through ultraviolet lamp camera bellows,
Fluorescence intensity at angle tip is apparently higher than other positions, and congregational rate and fluorometric investigation result are as shown in Figure 1 b, can
To observe the fluorescence intensity at angle tip as six times or so of side edge fluorescence intensity.
Embodiment 2
Embodiment 1 can be optimized, select silica gel as 3D printing material.
The preparation of semiconductor nano: the toluene colloidal sol of Ag is prepared first: by 20mL oleic acid, 20mL oleyl amine and 0.34g
AgNO3It is added in flask, 5min is stirred at 30 DEG C, 0.08g Fe (NO is added later3)3·4H2O raises the temperature to 120 DEG C,
It is gradually warmed up stirring, the reaction was continued when being warming up to 120 DEG C 1h, addition volume ratio is 1:3 ethyl alcohol, is centrifuged later with 5000rpm
8min after sucking supernatant, precipitating obtained by bottom is dispersed in 14mL toluene, the toluene colloidal sol of 4nm Ag is obtained.
Then it prepares sulphur precursor solution: 10mL oleyl amine, 20mL oleic acid and 128mg sulphur powder being placed in flask, in room
The lower stirring of temperature is stirred to react 40min at 100 DEG C, is added 30ml toluene thereto, it is to be mixed uniformly after, it is molten to obtain sulphur presoma
Liquid.
Ag2The preparation of S nano particle colloidal sol: the toluene colloidal sol of the monodispersed 5nm Ag of 350 μ L is taken to burn in the round bottom of 25mL
In bottle, 6mL toluene and 3mL sulphur precursor solution are added thereto, reacts 1h in 50 DEG C of stirred in water bath, appropriate second is added
Alcohol obtains monodispersed Ag with 6000rpm centrifuge washing 10min2S nano particle.It distributes it in 6-10m1 toluene, obtains
To Ag2The toluene colloidal sol of S nano particle.
The CdS of Ag doping nanocrystalline preparation: by monodispersed Ag obtained above2S nano particle colloidal sol, is being stirred
Under, 0.2mL oleic acid, 0.1mL oleyl amine and suitable Cd (NO is added3)2·4H2O methanol solution (0.1g/m1), magnetic force stirs at room temperature
3min is mixed, 0.1mLTBP is added, reacts 2h in 60 DEG C of stirred in water bath, ethyl alcohol is added and is obtained with 5000rpm centrifuge washing 8min
Obtain CdS:Ag doped quantum dot.
Printing slurry configuration: the high-purity C dS:Ag doped quantum dot of preparation is dissolved in 1mL chloroform, 5g high-performance is added
Silica gel, mechanical stirring is uniform, obtains 3D printing slurry.
3D printing molding: the slurry of preparation is put into printer charging basket, is chosen the printing head that diameter is 0.2mm, is used
Computer manufacture 3D model, and carry out the parameter setting, print speed 15mm/s such as being sliced, print temperature is 25 DEG C, and printing is flat
Platform height is 0.18mm, carries out 3D printing, obtains flexible matrix semiconductor nano devices semi-finished product.
Use printing type for the shape changeable of construction different angle in the present embodiment: triangle (60 °), quadrangle (90 °)
With hexagon (120 °), printing shaping obtains fluorescence enhancement device, and as shown in Figure 2 b, fluorescence intensity can be with the increasing of device angles
Add and weaken, to reach controllable to the fluorescence intensity at endpoint.
Semi-finished product solidification: semi-finished product will be obtained and be put into baking oven, 80 DEG C of drying 20h, after taking-up it is available flexibility more preferably,
It can stablize and the semiconductor nano devices of shape is kept to carry out the test of fluorescence intensity to it, as a result as shown in Figure 2 b
Show that fluorescence intensity is six times of side edge or so at triangle (60 °) device endpoint, fluorescence is strong at quadrangle (90 °) endpoint
Degree is four times of side-walls or so, and fluorescence intensity is two times of side edge fluorescence intensity or so at hexagon (120 °) endpoint, fluorescence
Linear relationship is presented in intensity and shape changeable angle, to achieve the effect that controllable fluorescent.
Embodiment 3
The present embodiment prepares flexible matrix semiconductor nano device by taking doped quantum dot ZnS:Ag as an example.
The preparation of semiconductor nano: the toluene colloidal sol of Ag is prepared first: by 20mL oleic acid, 20mL oleyl amine and 0.34g
AgNO3It is added in flask, 5min is stirred at 30 DEG C, 0.08g Fe (NO is added later3)3·4H2O raises the temperature to 120 DEG C,
It is gradually warmed up stirring, the reaction was continued when being warming up to 120 DEG C 1h, addition volume ratio is 1:3 ethyl alcohol, is centrifuged later with 5000rpm
8min after sucking supernatant, precipitating obtained by bottom is dispersed in 14mL toluene, the toluene colloidal sol of 4nmAg is obtained.
Then ZnS:Ag quantum dot solution is prepared: by 0.15mmol ZnCl2, 200 μ L oleyl amines, 30 μ L tributyl phosphorus and 6mL
Toluene is fitted into three-necked bottle, and mixture is heated to 100 DEG C under argon gas, injects 200 μ L mercaptan ligands, injection 1mL preparation
Ag2Excessive oleic acid is added into said mixture in S precursor solution, removes unreacted metal sulfate ester, be added acetone or
Ethyl alcohol is centrifuged 8min with 5000rpm, and after sucking supernatant, 10mL toluene is added in precipitating, obtains ZnS:Ag doped quantum dot solution.
Print slurry configuration: in 50 DEG C of water-baths under heating state, the high-purity ZnS:Ag doped quantum dot of preparation is molten
In 1mL chloroform, 2.5g polylactic acid is added, adding 5mL chloroform is uniformly mixed polylactic acid dissolution with doped quantum dot, and
Lasting stirring, until system occurs thick, whens flow difficulties, stops heating, and taking-up obtains 3D printing slurry.
3D printing molding: the slurry of preparation is put into printer charging basket, is chosen the printing head that diameter is 0.2mm, is used
Computer manufacture 3D model, and carry out the parameter setting, print speed 10mm/s such as being sliced, print temperature is 25 DEG C, and printing is flat
Platform height is 0.18mm, carries out 3D printing, obtains flexible matrix semiconductor nano devices semi-finished product.
In the present embodiment, the printing path used, which orients for each layer along parallel path, to be printed, and printing multilayer obtains block
As shown in Figure 3a.
Semi-finished product solidification: the present embodiment is using polylactic acid printed material, and drying at room temperature is stood after printing
Curing molding, while having stable fluorescent effect carries out the test of fluorescence intensity to the device after solidification, such as Fig. 3 b, in parallel
Two times of the fluorescence intensity on Print direction are perpendicular in the fluorescence intensity on Print direction.
Embodiment 4
Embodiment 3 can be optimized, select silica gel as 3D printing material.
The preparation of semiconductor nano: the toluene colloidal sol of Ag is prepared first: by 20mL oleic acid, 20mL oleyl amine and 0.34g
AgNO3It is added in flask, 5min is stirred at 30 DEG C, 0.08g Fe (NO is added later3)3·4H2O raises the temperature to 120 DEG C,
It is gradually warmed up stirring, the reaction was continued when being warming up to 120 DEG C 1h, addition volume ratio is 1:3 ethyl alcohol, is centrifuged later with 5000rpm
8min after sucking supernatant, precipitating obtained by bottom is dispersed in 14mL toluene, the toluene colloidal sol of 4nm Ag is obtained.
Then ZnS:Ag doped quantum dot solution is prepared: by 0.15mmol ZnCl2, 200 μ L oleyl amines, 30 μ L, tri- fourth phosphine and
6mL toluene is fitted into three-necked bottle, and mixture is heated to 100 DEG C under argon gas, injects 200 μ L mercaptan ligands, injection 1mL preparation
Ag2Excessive oleic acid is added into said mixture in S precursor solution, removes unreacted metal sulfate ester, be added acetone or
Ethyl alcohol is centrifuged 8min with 5000rpm, and after sucking supernatant, 10mL toluene is added in precipitating, obtains ZnS:Ag doped quantum dot solution.
Printing slurry configuration: the high-purity ZnS:Ag doped quantum dot of preparation is dissolved in 1mL chloroform, 2.5g high is added
Energy silica gel, mechanical stirring is uniform, obtains 3D printing slurry.
3D printing molding: the slurry of preparation is put into printer charging basket, is chosen the printing head that diameter is 0.2mm, is used
Computer manufacture 3D model, and carry out the parameter setting, print speed 15mm/s such as being sliced, print temperature is 25 DEG C, and printing is flat
Platform height is 0.18mm, carries out 3D printing, obtains flexible matrix semiconductor nano devices semi-finished product.
In the present embodiment, using printing path same as Example 3, the printing path used is each floor along parallel road
Diameter orientation printing, printing multilayer obtain block, and as shown in 4a, gained block is identical as the block in embodiment 3, but doping
The content of son point is twice of 3 kinds of embodiment of block.
Semi-finished product solidification: semi-finished product will be obtained and be put into baking oven, 80 DEG C of drying 20h, after taking-up it is available flexibility more preferably,
The semiconductor nano devices for keeping shape can be stablized, while there is stable fluorescent effect, this and 3 class of embodiment
Seemingly, glimmering it can be observed that being apparently higher than along the fluorescence intensity on Print direction perpendicular to the fluorescence intensity on Print direction
Intensity measurements are as shown in Figure 4 b, the fluorescence intensity being perpendicular on Print direction along the fluorescence intensity on Print direction
Two times, this illustrates that the technology is unrelated with the content of doped quantum dot, have universal usability.
Embodiment 5
The present embodiment prepares flexible matrix semiconductor nano device by taking doped quantum dot CdS:Cu as an example.
The preparation of semiconductor nano: copper stearate powder is prepared first: 70mL n-hexane, 5mmol (1.5323g) is hard
Resin acid sodium is placed in 250mL round-bottomed flask and stirs 3min, and 40mL methanol is then added and continues to stir 3min.Prepare 10mL's
The Copper dichloride dihydrate methanol solution of 0.25mol/L simultaneously instills in above-mentioned mixed solution.It is eventually adding 10mL high purity water, 52 DEG C of water
It is stirred to react 4h in bath, takes out flask lower layer blue copper stearate, proper amount of methanol is added, 5500r centrifuge washing 8min is placed in 60
Drying and grind into powder in DEG C baking oven.
Then Cu is prepared2S is nanocrystalline: taking the above-mentioned copper stearate powder of 0.25mmol (157.7mg), 5mL oleic acid, 3mL oil
Amine is placed in 10mL reaction kettle and stirs 5min, takes 0.25mL n- dodecyl mereaptan to be added in above-mentioned mixed liquor, stirs evenly, and seals
It is placed on 2.5h in 200 DEG C of baking ovens well, takes brown solution 1:3 ethyl alcohol 5500r centrifuge washing 8min, is then distributed to 8mL toluene
In.
Preparation Cu adulterates CdS quantum dot: taking the above-mentioned Cu of 8mL2The 0.1g/mL Cd of S nanocrystalline toluene colloidal sol and 1mL
(NO3)2·4H2O methanol solution, is placed in the round-bottomed flask of 25mL and stirs evenly, and the TBP of 0.1mL is then added, in 56 DEG C of water
It is stirred to react 2h in bath, ethanol in proper amount is added, 6500r centrifuge washing 8min is distributed in 1mL toluene and gets product.Above-mentioned
It can be by regulating and controlling Cd in step2+The CdS that additional amount and the temperature of reaction synthesize different Cu doped in concentrations profiled is nanocrystalline.
Print slurry configuration: in 50 DEG C of water-baths under heating state, the high-purity C dS:Cu doped quantum dot of preparation is molten
In 1mL chloroform, 2.5g polylactic acid is added, adding 5mL chloroform is uniformly mixed polylactic acid dissolution with doped quantum dot, and
Lasting stirring, until system occurs thick, whens flow difficulties, stops heating, and taking-up obtains 3D printing slurry.
3D printing molding: the slurry of preparation is put into printer charging basket, is chosen the printing head that diameter is 0.12mm, is used
Computer manufacture 3D model, and carry out the parameter setting, print speed 8mm/s such as being sliced, print temperature is 25 DEG C, print platform
Height is 0.1mm, carries out 3D printing, obtains flexible matrix semiconductor nano devices semi-finished product.
In the present embodiment, the printing path used is staggeredly printing type, and vertically path prints adjacent two layers, can
To obtain isotropic device, wherein a specific face or specific one layer of fluorescence can be made to assemble enhancing, this face or this
Layer is printed using along with adjacent layer parallel direction, can achieve the purpose of fluorescence enhancement.
Semi-finished product solidification: the present embodiment is using polylactic acid printed material, and drying at room temperature is stood after printing
Curing molding, while there is stable fluorescent effect, device is placed under the irradiation of ultraviolet light, it can be observed that edge and adjacent layer
That layer or side fluorescence intensity of parallel direction printing are remarkably reinforced, and have reached the control of the fluorescence intensity of opposite or layer.
Embodiment 6
Embodiment 5 can be optimized, select silica gel as 3D printing material.
The preparation of semiconductor nano: copper stearate powder is prepared first: 70mL n-hexane, 5mmol (1.5323g) is hard
Resin acid sodium is placed in 250mL round-bottomed flask and stirs 3min, and 40mL methanol is then added and continues to stir 3min.Prepare 10mL's
The Copper dichloride dihydrate methanol solution of 0.25mol/L simultaneously instills in above-mentioned mixed solution.It is eventually adding 10mL high purity water, 52 DEG C of water
It is stirred to react 4h in bath, takes out flask lower layer blue copper stearate, proper amount of methanol is added, 5500r centrifuge washing 8min is placed in 60
Drying and grind into powder in DEG C baking oven.
Then Cu is prepared2S is nanocrystalline: taking the above-mentioned copper stearate powder of 0.25mmol (157.7mg), 5mL oleic acid, 3mL oil
Amine is placed in 10mL reaction kettle and stirs 5min, takes 0.25mL n- dodecyl mereaptan to be added in above-mentioned mixed liquor, stirs evenly, and seals
It is placed on 2.5h in 200 DEG C of baking ovens well, takes brown solution 1:3 ethyl alcohol 5500r centrifuge washing 8min, is then distributed to 8mL toluene
In.
Preparation Cu adulterates CdS quantum dot: taking the above-mentioned Cu of 8mL2The 0.1g/mL Cd of S nanocrystalline toluene colloidal sol and 1mL
(NO3)2·4H2O methanol solution, is placed in the round-bottomed flask of 25mL and stirs evenly, and the TBP of 0.1mL is then added, in 56 DEG C of water
It is stirred to react 2h in bath, ethanol in proper amount is added, 6500r centrifuge washing 8min is distributed in 1mL toluene and gets product.Above-mentioned
It can be by regulating and controlling Cd in step2+The CdS that additional amount and the temperature of reaction synthesize different Cu doped in concentrations profiled is nanocrystalline.
Printing slurry configuration: the high-purity C dS:Cu doped quantum dot of preparation is dissolved in 1mL chloroform, 5g high-performance is added
Silica gel, mechanical stirring is uniform, obtains 3D printing slurry.
3D printing molding: the slurry of preparation is put into printer charging basket, is chosen the printing head that diameter is 0.16mm, is used
Computer manufacture 3D model, and carry out the parameter setting, print speed 12mm/s such as being sliced, print temperature is 25 DEG C, and printing is flat
Platform height is 0.14mm, carries out 3D printing, obtains flexible matrix semiconductor nano devices semi-finished product.
In the present embodiment, the printing path used is staggeredly printing type, and vertically path prints adjacent two layers, can
To obtain isotropic device, wherein a specific point fluorescence aggregation enhancing can be made, 60 ° of angle are constructed at this point
Structure, remaining path is constant, achievees the purpose that fluorescence enhancement.
Semi-finished product solidification: semi-finished product will be obtained and be put into baking oven, 80 DEG C of drying 20h, after taking-up it is available flexibility more preferably,
The semiconductor nano devices for keeping shape can be stablized, while there is stable fluorescent effect, device is placed on purple
Under the irradiation of outer lamp, it can be observed that fluorescence enhancement at specified point, has reached the control to the fluorescence intensity of arbitrary point.
Embodiment 7
The present embodiment prepares flexible matrix semiconductor nano device by taking doped quantum dot CdS:Cu as an example.
The preparation of semiconductor nano: copper stearate powder is prepared first: 70mL n-hexane, 5mmol (1.5323g) is hard
Resin acid sodium is placed in 250mL round-bottomed flask and stirs 3min, and 40mL methanol is then added and continues to stir 3min.Prepare 10mL's
The Copper dichloride dihydrate methanol solution of 0.25mol/L simultaneously instills in above-mentioned mixed solution.It is eventually adding 10mL high purity water, 52 DEG C of water
It is stirred to react 4h in bath, takes out flask lower layer blue copper stearate, proper amount of methanol is added, 5500r centrifuge washing 8min is placed in 60
Drying and grind into powder in DEG C baking oven.
Then Cu is prepared2S is nanocrystalline: taking the above-mentioned copper stearate powder of 0.25mmol (157.7mg), 5mL oleic acid, 3mL oil
Amine is placed in 10mL reaction kettle and stirs 5min, takes 0.25mL n- dodecyl mereaptan to be added in above-mentioned mixed liquor, stirs evenly, and seals
It is placed on 2.5h in 200 DEG C of baking ovens well, takes brown solution 1:3 ethyl alcohol 5500r centrifuge washing 8min, is then distributed to 8mL toluene
In.
Preparation Cu adulterates CdS quantum dot: taking the above-mentioned Cu of 8mL2The 0.1g/mL Cd of S nanocrystalline toluene colloidal sol and 1mL
(NO3)2·4H2O methanol solution, is placed in the round-bottomed flask of 25mL and stirs evenly, and the TBP of 0.1mL is then added, in 56 DEG C of water
It is stirred to react 2h in bath, ethanol in proper amount is added, 6500r centrifuge washing 8min is distributed in 1mL toluene and gets product.Above-mentioned
It can be by regulating and controlling Cd in step2+The CdS that additional amount and the temperature of reaction synthesize different Cu doped in concentrations profiled is nanocrystalline.
Print slurry configuration: in 50 DEG C of water-baths under heating state, the high-purity C dS:Cu doped quantum dot of preparation is molten
In 1mL chloroform, 2.5g polylactic acid is added, adding 5mL chloroform is uniformly mixed polylactic acid dissolution with doped quantum dot, and
Lasting stirring, until system occurs thick, whens flow difficulties, stops heating, and taking-up obtains 3D printing slurry.
3D printing molding: the slurry of preparation is put into printer charging basket, is chosen the printing head that diameter is 0.12mm, is used
Computer manufacture 3D model, and carry out the parameter setting, print speed 8mm/s such as being sliced, print temperature is 25 DEG C, print platform
Height is 0.1mm, carries out 3D printing, obtains flexible matrix semiconductor nano devices semi-finished product.
In the present embodiment, for the printing path used for a series of concentric loop structures, obtained device is as shown in Figure 5.
Semi-finished product solidification: the present embodiment is using polylactic acid printed material, and drying at room temperature is stood after printing
Curing molding, while there is stable fluorescent effect, device is placed under the irradiation of ultraviolet light, is observed glimmering on different directions
Luminous intensity is different, as shown in figure 5 a and 5b.
Embodiment 8
The present embodiment is with core-shell structure Au@HgxCd1-xFor Te is nanocrystalline, flexible matrix semiconductor nano device is prepared
Part.
The preparation of semiconductor nano:
Au@Ag2The preparation of Te precursor solution:
By 10mL Au@Ag precursor solution and 1.2mL Te presoma (take 30mg Te powder to be dissolved in 15mL hydrazine hydrate,
4h is heated in autoclave, forms homogeneous phase solution) 2min is mixed dropwise, acquired solution stands 30min in 30 DEG C of water-baths.
Product removes supernatant after 8000r/min is centrifuged 10min, and precipitating is dispersed again in deionized water, obtains Au Ag2Before Te
Drive liquid solution.
Au@Ag3AuTe2The preparation of precursor solution:
In Au@Ag2Cetyl trimethylammonium bromide (CTAB) solution of 1mL is added in Te precursor solution, is heated to
45 DEG C, 2min is kept the temperature, the Cd (NO of 0.05mL is added3)2Solution (30mg/mL) stirs 2min, vibrates lower three fourths that 30 μ l are added
Base phosphine (TBP).Solution is in 45 DEG C of standing 30min.Products therefrom removes supernatant, precipitating after 8000r/min is centrifuged 10min
It is scattered in deionized water, obtains Au@Ag3AuTe2Precursor solution.
The preparation of Au@CdTe precursor solution:
To Au@Ag3AuTe21mL CTAB solution (0.2M) is added in precursor solution, preheats 5min in 60 DEG C of water-baths,
Cd (the NO of 1mL 30mg/mL is added3)2Solution.It is slowly stirred 2min, vibrates 2min, the TBP of 60 μ l is added.In 60 DEG C of water-baths
Stand 2h.It is centrifuged 10min with 8000r/min, removes supernatant, precipitating dispersion in deionized water, obtains Au CdTe presoma
Solution is similar.
Au@HgxCd1-XTe nanocrystalline preparation:
0.5mL CTAC solution (0.2M) is added in Au@CdTe precursor solution, is slowly stirred 1min, HgCl is added2
(5mg/mL) solution.After solution stands 0.5h at 25 DEG C with 8000r/min centrifugation 10min, supernatant is removed, precipitating is scattered in
In deionized water, Au@Hg is obtainedxCd1-XTe is nanocrystalline.
Print slurry configuration: by the Au@Hg of preparationxCd1-XTe is nanocrystalline to be dissolved in a small amount of chloroform, a dozen printing paste material are added
Configuration: in 50 DEG C of water-baths under heating state, by the Au@Hg of preparationxCd1-XTe is nanocrystalline to be dissolved in 1mL chloroform, and 2.5g is added
Polylactic acid, adding 5mL chloroform is uniformly mixed polylactic acid dissolution with doped quantum dot, and continues to stir, until system goes out
Existing thick, whens flow difficulties, stops heating, and taking-up obtains 3D printing slurry.
3D printing molding: the slurry of preparation is put into printer charging basket, is chosen the printing head that diameter is 0.21mm, is used
Computer manufacture 3D model, and carry out the parameter setting, print speed 10mm/s such as being sliced, print temperature is 25 DEG C, and printing is flat
Platform height is 0.18mm, carries out 3D printing, obtains flexible matrix semiconductor nano devices semi-finished product, different by setting
Program, the device of construction triangle (60 °), quadrangle (90 °) and hexagon (120 °).
Semi-finished product solidification: the present embodiment is using polylactic acid printed material, and drying at room temperature is stood after printing
Curing molding, the flexible device of preparation have surface plasma body resonant vibration characteristic in the near infrared region, have apparent visible light-
Near infrared from detecting characteristic, wherein infrared characteristic enhances as device angles are reduced, similar with embodiment before, illustrates the present invention
It is applicable not only to fluorescent device, also can be applied to infrared acquisition field.
Embodiment 9
Embodiment 8 can be optimized, select silica gel as 3D printing material.
The preparation of semiconductor nano:
Au@Ag2The preparation of Te precursor solution:
By 10mL Au@Ag precursor solution and 1.2mL Te presoma (take 30mg Te powder to be dissolved in 15mL hydrazine hydrate,
4h is heated in autoclave, forms homogeneous phase solution) 2min is mixed dropwise, acquired solution stands 30min in 30 DEG C of water-baths.
Product removes supernatant after 8000r/min is centrifuged 10min, and precipitating is dispersed again in deionized water, obtains Au Ag2Before Te
Drive liquid solution.
Au@Ag3AuTe2The preparation of precursor solution:
In Au@Ag2Cetyl trimethylammonium bromide (CTAB) solution of 1mL is added in Te precursor solution, is heated to
45 DEG C, 2min is kept the temperature, the Cd (NO of 0.05mL is added3)2Solution (30mg/mL) stirs 2min, vibrates lower three fourths that 30 μ l are added
Base phosphine (TBP).Solution is in 45 DEG C of standing 30min.Products therefrom removes supernatant, precipitating after 8000r/min is centrifuged 10min
It is scattered in deionized water, obtains Au@Ag3AuTe2Precursor solution.
The preparation of Au@CdTe precursor solution:
To Au@Ag3AuTe21mL CTAB solution (0.2M) is added in precursor solution, preheats 5min in 60 DEG C of water-baths,
Cd (the NO of 1mL 30mg/mL is added3)2Solution.It is slowly stirred 2min, vibrates 2min, the TBP of 60 μ l is added.In 60 DEG C of water-baths
Stand 2h.It is centrifuged 10min with 8000r/min, removes supernatant, precipitating dispersion in deionized water, obtains Au CdTe presoma
Solution is similar.
Au@HgxCd1-XTe nanocrystalline preparation:
0.5mL CTAC solution (0.2M) is added in Au@CdTe precursor solution, is slowly stirred 1min, HgCl is added2
(5mg/mL) solution.After solution stands 0.5h at 25 DEG C with 8000r/min centrifugation 10min, supernatant is removed, precipitating is scattered in
In deionized water, Au@Hg is obtainedxCd1-XTe is nanocrystalline.
Print slurry configuration: by the Au@Hg of preparationxCd1-XTe is nanocrystalline to be dissolved in 1mL toluene, and 5g high performance silicon is added
Glue, mechanical stirring is uniform, obtains 3D printing slurry.
3D printing molding: the slurry of preparation is put into printer charging basket, is chosen the printing head that diameter is 0.21mm, is used
Computer manufacture 3D model, and carry out the parameter setting, print speed 10mm/s such as being sliced, print temperature is 25 DEG C, and printing is flat
Platform height is 0.18mm, carries out 3D printing, obtains flexible matrix semiconductor nano devices semi-finished product, the print path of use
Diameter is that each layer is printed along parallel path orientation, obtains isotropic bulk devices.
Semi-finished product solidification: semi-finished product will be obtained and be put into baking oven, 80 DEG C of drying 20h, after taking-up it is available flexibility more preferably,
The semiconductor nano devices for keeping shape can be stablized.The flexible device of preparation have in the near infrared region surface etc. from
Daughter resonance characteristics has apparent visible light-near infrared from detecting characteristic, and wherein infrared characteristic increases as device angles are reduced
By force, as a result show to be better than the infrared property perpendicular to Print direction along the infrared property on Print direction simultaneously, it is red to optimizing
Outer device is of great significance.
Above-described specific descriptions have carried out further specifically the purpose of invention, technical scheme and beneficial effects
It is bright, it should be understood that the above is only a specific embodiment of the present invention, the protection model being not intended to limit the present invention
It encloses, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the present invention
Protection scope within.
Claims (9)
1. a kind of 3D printing method of intensity controlled semiconductor nano flexible photoelectric device, it is characterised in that: including following step
It is rapid:
(1) preparation of semiconductor nano: semiconductor nano includes the size of liquid phase reactor preparation, the monodispersed quantum of pattern
Point, doped quantum dot and heterogeneous structural nano are brilliant；It is prepared using hot injection method or low temperature cationic exchange process, and can
Semiconductor nano is reached by regulation surface ligand to be distributed in different solvents；
(2) it 3D printing slurry preparation: disperses semiconductor nano in and obtains semiconductor in organic solvent or inorganic solvent and receive
The colloidal sol is uniformly mixed with the flexible matrix with the rheological equationm of state, obtains 3D printing slurry by the brilliant colloidal sol of rice；
(3) three 3D printing flexible matrix semiconductor nano device: are carried out to obtained slurry by direct write 3D printing technique
Shaping structures are tieed up, semiconductor nano device semi-finished product is formed, designs different path angles, Neng Goushi according to different needs
Now to specified point, the control of performance, structural anisotropy's device in certain surface；
(4) flexible matrix semiconductor nano device solidifies: the semiconductor nano device semi-finished product are dried, so that
It is formed by curing stable semiconductor nano device.
2. a kind of 3D printing method of intensity controlled semiconductor nano flexible photoelectric device as described in claim 1, special
Sign is: in step (1), the semiconductor nano is that the Ag of liquid phase method preparation adulterates CdS, and Cu adulterates CdS, Ag doping
CdSe, Cu adulterate CdSe, and Ag adulterates ZnS, and Cu adulterates ZnS, Au-HgxCd1-xTe core-shell nano is brilliant, and Au-CdS core-shell nano is brilliant.
3. a kind of 3D printing method of intensity controlled semiconductor nano flexible photoelectric device as described in claim 1, special
Sign is: the nanocrystalline device of flexible semiconductor made by adding curing agent is able to maintain that stable shape；Have in configuration
Curing agent is added when having the flexible matrix of the rheological equationm of state；The curing agent of addition and the mass ratio of flexible matrix are not more than 10%.
4. a kind of 3D printing method of intensity controlled semiconductor nano flexible photoelectric device as described in claim 1, special
Sign is: the semiconductor nano concentration in the semiconductor nanocrystalline sol is 10wt% to 99wt%；The semiconductor is received
The brilliant colloidal sol of rice and the mass ratio of flexible matrix are not more than 10%.
5. a kind of 3D printing method of intensity controlled semiconductor nano flexible photoelectric device as described in claim 1, special
Sign is: jet diameters range described in step (3) is 0.01~0.5mm printing precision according to actual needs, is chosen corresponding
The spray head of size；Print speed is between 5~20mm/s.
6. a kind of 3D printing method of intensity controlled semiconductor nano flexible photoelectric device as described in claim 1, special
Sign is: print platform and nozzle distance can choose 0.02~0.4mm when the jet diameters range is 0.01~0.5mm.
7. a kind of 3D printing method of intensity controlled semiconductor nano flexible photoelectric device as claimed in claim 5, special
Sign is: under the conditions of jet diameters 0.2mm, print platform height and nozzle distance are 0.16mm.
8. a kind of 3D printing method of intensity controlled semiconductor nano flexible photoelectric device as claimed in claim 5, special
Sign is: the print speed is 10mm/s.
9. a kind of 3D printing method of intensity controlled semiconductor nano flexible photoelectric device as described in claim 1, special
Sign is: the path: for different demands, by designing different printing paths, or the printing angle that construction is different
Realize that device, and the angle of printing path is smaller in the quantitative enhancing of certain point or certain one side, reinforcing effect is more obvious, from
And realize the regulation to performance.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112071927A (en) * | 2020-08-27 | 2020-12-11 | 深圳市奥伦德元器件有限公司 | Infrared detector and preparation method thereof |
| CN114013028A (en) * | 2021-11-03 | 2022-02-08 | 北京理工大学 | Method for constructing semiconductor nanocrystalline device microstructure with highlight overflow effect |
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| CN106601896A (en) * | 2016-12-22 | 2017-04-26 | 广东轩朗实业有限公司 | Quantum dot encapsulation structure and preparation method thereof, and glass quantum dot diffusion plate |
| CN107056974A (en) * | 2016-03-10 | 2017-08-18 | 北京理工大学 | A kind of preparation method of nanocrystal/polymer solid solution |
| CN107583106A (en) * | 2017-09-15 | 2018-01-16 | 东华大学 | Poly- citrate/chitin nano whisker tissue engineering bracket and preparation method thereof |
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| CN104701138A (en) * | 2015-03-08 | 2015-06-10 | 北京工业大学 | Preparation method for CZTS (Se) nano-crystalline thin film |
| CN107056974A (en) * | 2016-03-10 | 2017-08-18 | 北京理工大学 | A kind of preparation method of nanocrystal/polymer solid solution |
| CN106601896A (en) * | 2016-12-22 | 2017-04-26 | 广东轩朗实业有限公司 | Quantum dot encapsulation structure and preparation method thereof, and glass quantum dot diffusion plate |
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| CN112071927A (en) * | 2020-08-27 | 2020-12-11 | 深圳市奥伦德元器件有限公司 | Infrared detector and preparation method thereof |
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| CN114013028A (en) * | 2021-11-03 | 2022-02-08 | 北京理工大学 | Method for constructing semiconductor nanocrystalline device microstructure with highlight overflow effect |
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