CN108269923A - A kind of quantum point probe and preparation method thereof - Google Patents

A kind of quantum point probe and preparation method thereof Download PDF

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CN108269923A
CN108269923A CN201611262012.7A CN201611262012A CN108269923A CN 108269923 A CN108269923 A CN 108269923A CN 201611262012 A CN201611262012 A CN 201611262012A CN 108269923 A CN108269923 A CN 108269923A
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quantum
dot
layer
presoma
structure unit
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曹蔚然
刘政
杨行
杨一行
钱磊
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TCL Corp
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
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    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract

The present invention discloses a kind of quantum point probe and preparation method, and the quantum point probe includes successively：Conductive substrates, hole injection layer, quantum dot active layer, electron transfer layer and top electrode；The material of the quantum dot active layer is quanta point material, it includes at least one quantum-dot structure unit arranged successively in radial directions, graded alloy component structure or in the radial direction level width consistent homogeneous components structure of the quantum-dot structure unit for the variation of radial direction level width.By the present invention in that by the use of quanta point material and by the use of quanta point material as quantum dot active layer, both detectivity, the quantum efficiency of quantum point probe had been improved, the dark current of quantum point probe is also reduced, while simplifies device architecture, saves cost of manufacture.

Description

A kind of quantum point probe and preparation method thereof
Technical field
The present invention relates to field of photodetectors more particularly to a kind of quantum point probe and preparation method thereof.
Background technology
Photodetector is to utilize a kind of light-detecting device made of the photoconductive effect of semi-conducting material, so-called photoconduction Effect, refers to a kind of physical phenomenon for illuminated material electric conductivity being caused to change by radiation, and photodetector can turn optical signal It is changed to electric signal.
As New Generation Optical electric material, quantum dot（Quantum dot）Extensive concern is obtained when with unique property. Quantum dot light electric explorer（Quantum dot photodetectors）With to vertical incidence photaesthesia, photoconductive response degree It is high, specific detecivity is high, detection wavelength is continuously adjusted and the advantages that low temperature preparation.In general, photoelectric diode structure quantum dot Detector can be divided into Schottky type again（Schottky-type）, heterojunction type（heterojunction type）, p-n junction（p-n type）With p-i-n types（p-i-n type）Structure.Compared with photoconductor structure, the quantum dot optoelectronic of photoelectric diode structure Detector is with the obvious advantage in terms of response speed, has faster response speed, and this quantum dot light electric explorer exists In operational process, quantum dot light photosensitive layer absorbs after photon the photo-generate electron-hole that generates to can be under the action of built in field It detaches, this causes the feature detector to have lower driving voltage, can be in low applying bias even zero applying bias It is lower just to work, and easily controllable.
Although the quantum dot part of nucleocapsid improves quantum dot performance in the prior art, no matter from mentality of designing also It is from prioritization scheme or from the aspect of the efficiency based on promotion quantum dot itself, performance need to be improved, for example, existing Its detectivity of some photodetectors and quantum efficiency are relatively low, and the prior art does not also consider photodetector For other aspect particular/special requirements of quanta point material.
Therefore, the prior art has yet to be improved and developed.
Invention content
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of quantum point probe and its preparation sides Method, it is intended to solve the problems, such as that existing detector its detectivity, quantum efficiency are to be improved.
Technical scheme is as follows：
A kind of quantum point probe, wherein, include successively：Conductive substrates, hole injection layer, quantum dot active layer, electron-transport Layer and top electrode；The material of the quantum dot active layer is quanta point material, including it is at least one in radial directions successively The quantum-dot structure unit of arrangement, the quantum-dot structure unit are the graded alloy component knot of radial direction level width variation The consistent homogeneous components structure of structure or in the radial direction level width.
The quantum point probe, wherein, one layer of sky is provided between the hole injection layer and quantum dot active layer Cave transport layer.
The quantum point probe, wherein, the quantum-dot structure unit be in the radial direction more outside energy level it is wide The wider graded alloy component structure of degree, and the quantum-dot structure unit of graded alloy component structure adjacent in radial directions Energy level be continuous.
The quantum point probe, wherein, the quanta point material is arranged successively in radial directions including at least three The quantum-dot structure unit of cloth, wherein, in at least three quantum-dot structures unit, the quantum dot knot positioned at center and surface Structure unit is the graded alloy component structure that more outside level width is wider in the radial direction, and adjacent in radial directions The energy level of the quantum-dot structure unit of graded alloy component structure is continuous；Quantum-dot structure unit positioned at center and surface Between a quantum-dot structure unit be homogeneous components structure.
The quantum point probe, wherein, the quanta point material includes two kinds of quantum-dot structure unit, In a type of quantum-dot structure unit be the wider graded alloy component structure of more outside level width in the radial direction, separately A type of quantum-dot structure unit is the narrower graded alloy component structure of more outside level width in the radial direction, described Two kinds of quantum-dot structure unit is radially alternately distributed successively, and graded alloy group adjacent in radial directions The energy level of the quantum-dot structure unit of separation structure is continuous.
The quantum point probe, wherein, the quantum-dot structure unit be in the radial direction more outside energy level it is wide The wider graded alloy component structure of degree, and the energy level of adjacent quantum-dot structure unit is discontinuous.
The quantum point probe, wherein, the quantum-dot structure unit be in the radial direction more outside energy level it is wide The narrower graded alloy component structure of degree, and the energy level of adjacent quantum-dot structure unit is discontinuous.
The quantum point probe, wherein, the quanta point material includes two amounts point structural unit, one of which Quantum-dot structure unit is the wider graded alloy component structure of more outside level width in the radial direction, another quantum dot knot Structure unit is homogeneous components structure, and the inside of the quanta point material includes one or more graded alloy component structure Quantum-dot structure unit, and the energy level of the quantum-dot structure unit of graded alloy component structure adjacent in radial directions is Continuously；The outside of the quanta point material includes the quantum-dot structure unit of one or more homogeneous components structure.
The quantum point probe, wherein, the quanta point material includes two amounts point structural unit, one of which Quantum-dot structure unit is homogeneous components structure, another quantum-dot structure unit for more outside level width in the radial direction more Wide graded alloy component structure, the inside of the quanta point material include the amount of one or more homogeneous components structure Son point structural unit, the outside of the quanta point material includes the quantum dot of one or more graded alloy component structure Structural unit, and the energy level of the quantum-dot structure unit of graded alloy component structure adjacent in radial directions is continuous.
The quantum point probe, wherein, the quantum-dot structure unit is the gradual change comprising II races and VI races element Alloy compositions structure or uniform alloy compositions structure.
The quantum point probe, wherein, the quantum-dot structure unit includes 2-20 layers of monoatomic layer, Huo Zhesuo State the structure cell layer that quantum-dot structure unit includes 1-10 layers.
The quantum point probe, wherein, the glow peak wave-length coverage of the quanta point material is 400 nanometers to 700 Nanometer.
The quantum point probe, wherein, the peak width at half height of the glow peak of the quanta point material is 12 nanometers to 80 Nanometer.
A kind of preparation method of quantum point probe as described above, wherein, including step：
A, one layer of hole injection layer is deposited on conductive substrates；
B, one layer of quantum dot active layer is deposited on hole injection layer；The material of the quantum dot active layer is quanta point material, The quanta point material includes at least one quantum-dot structure unit arranged successively in radial directions, the quantum-dot structure Graded alloy component structure or in the radial direction level width consistent uniform of the unit for the variation of level width in the radial direction Component structure；
C, one layer of electron transfer layer is deposited on quantum dot active layer；
D, one layer of top electrode is deposited on the electron transport layer, obtains quantum point probe.
The preparation method of the quantum point probe, wherein, it is further included after the step A, before B：
One layer of hole transmission layer is deposited on the hole injection layer.
Advantageous effect：By the present invention in that by the use of quanta point material and by the use of quanta point material as quantum dot active layer, both Detectivity, the quantum efficiency of quantum point probe are improved, also reduces the dark current of quantum point probe, is simplified simultaneously Device architecture saves cost of manufacture.
Description of the drawings
Fig. 1 is a kind of structure diagram of quantum point probe preferred embodiment of the present invention.
Fig. 2 is the level structure curve of quanta point material concrete structure 1 in quantum point probe of the present invention.
Fig. 3 is the level structure curve of quanta point material concrete structure 2 in quantum point probe of the present invention.
Fig. 4 is the level structure curve of quanta point material concrete structure 3 in quantum point probe of the present invention.
Fig. 5 is the level structure curve of quanta point material concrete structure 4 in quantum point probe of the present invention.
Fig. 6 is the level structure curve of quanta point material concrete structure 5 in quantum point probe of the present invention.
Fig. 7 is the level structure curve of quanta point material concrete structure 6 in quantum point probe of the present invention.
Fig. 8 is the level structure curve of quanta point material concrete structure 7 in quantum point probe of the present invention.
Fig. 9 is a kind of structure diagram of quantum point probe embodiment 33 of the present invention.
Specific embodiment
The present invention provides a kind of quantum point probe and preparation method, to make the purpose of the present invention, technical solution and effect Clearer, clear and definite, the present invention is described in more detail below.It should be appreciated that specific embodiment described herein is only To explain the present invention, it is not intended to limit the present invention.
Referring to Fig. 1, Fig. 1 is a kind of first structure schematic diagram of quantum point probe preferred embodiment of the present invention, such as scheme It is shown, include successively：Conductive substrates 11, hole injection layer 12, quantum dot active layer 13, electron transfer layer 14 and top electrode 15； The material of the quantum dot active layer 13 is quanta point material, including at least one quantum arranged successively in radial directions Point structural unit, graded alloy component structure or radial direction side of the quantum-dot structure unit for the variation of radial direction level width The consistent homogeneous components structure of upward level width.
The present invention utilizes the quantum dot of structure optimization, optimizes the level structure of quantum dot, can greatly reduce quantum The defects of putting surface state, the quantum point probe of this structure can effectively improve the quantum efficiency and detectivity of device.
Further, the device architecture wide variety of the quantum point probe can need to design different devices according to different Part structure can also form the quantum dot light electric explorer or photoelectronic detecting array of laminated construction by adding multiple device cells. In photoelectric diode structure, photo-generated carrier is generally required can just be collected by several device areas, therefore the thickness of device Spend it is most important, and the service life of carrier have to be larger than the haulage time of carrier.Since carrier is in quantum dot film With longer diffusion length, and state the defects of can greatly reduce quantum dot surface by ligand exchange, therefore it is this The photodetector of structure greatly increases the quantum efficiency of device（EQE）；
In photoelectric diode structure quantum dot light electric explorer, the dark current of Schottky type quantum point probe is larger, causes It has higher noise；And if setting N-shaped metal oxide between p-type quantum dot layer and Al electrodes（Such as ZnO, TiO2） As electron transfer layer, it is built into the quantum dot light electric explorer of p-n junction photoelectric diode structure, the structure and Schottky type knot Structure is compared, and dark current reduces about two orders of magnitude, and keeps low noise level and high detection sensitivity；
It is possible to further set electronic barrier layer and hole blocking layer respectively between quantum dot active layer and upper/lower electrode, Quantum dot light photosensitive layer is made to be clipped between p-type material and n-type material, sandwich structure is formed, is built into non-with solar battery structure Often similar p-i-n type structure quantum point photodetectors can greatly reduce the dark current of device and obtain very high Quantum efficiency（Can be more than 100%）And detectivity；
Unlike Schottky type structure, in p-i-n type structure quantum point photodetectors, quantum efficiency and detection are sensitive Degree increases substantially the reduction for being not as noise, but because in addition to the main photoelectric current of device in this structure（Primary photocurrent）Contribution outside, further include secondary photocurrent（Secondary photocurrent）Contribution, have device There are higher efficiency and responsiveness；
In addition to this, the quantum dot light electric explorer of photoelectric diode structure can be prepared, and can make by low temperature whole soln method It is standby into broad area device.Meanwhile in this configuration, also device can be improved through a variety of ways, such as optimizes quantum dot light The thickness of photosensitive layer realizes the device architecture of complete depletion type or introduces interface-modifying layer and carrier barrier layer in the device structure Deng so as to the EQE and detectivity that further reduce the dark current of device, improve device.
Further, in the present invention, as shown in Figure 1, the conductive substrates 11 refer to the substrate containing hearth electrode, wherein Hearth electrode may be selected from indium doping tin oxide（ITO）, fluorine-doped tin oxide（FTO）, antimony-doped tin oxide（ATO）, aluminium doping oxygen Change zinc（AZO）In it is one or more；Preferably, the conductive substrates are ITO.
Further, in the present invention, the material of the hole injection layer 12 is preferably PEDOT:PSS, the PEDOT:PSS Thickness be 10 ~ 50nm.
Further, one layer of hole transmission layer 16, institute are provided between the hole injection layer 12 and quantum dot active layer 13 The thickness for stating hole transmission layer 16 is 10 ~ 100 nm；The hole transmission layer 16 may be selected from having having for cavity transmission ability Machine material, including but not limited to poly- (9,9- dioctyl fluorene-CO-N- (4- butyl phenyls) diphenylamines)（TFB）, polyvinylcarbazole （PVK）, poly- (bis- bis- (phenyl) benzidine of (4- butyl phenyls)-N, N'- of N, N')（poly-TPD）, it is poly- (9,9- dioctyl fluorenes- Co- double-N, N- phenyl -1,4- phenylenediamines)（PFB）, 4,4 ', 4 ' '-three (carbazole -9- bases) triphenylamine（TCTA）, bis- (9- of 4,4'- Carbazole) biphenyl（CBP）, N, N '-diphenyl-N, N '-two (3- aminomethyl phenyls) -1,1 '-biphenyl -4,4 '-diamines（TPD）、N,N’- Diphenyl-N, N '-（1- naphthalenes）- 1,1 '-biphenyl -4,4 '-diamines（NPB）, doped graphene, undoped graphene, C60Or it Mixture；Preferably, the hole transmission layer 16 is poly-TPD；
Further, in the present invention, 14 material of electron transfer layer may be selected from the organic material with electron transport ability or Inorganic material, wherein, the organic material with electron transport ability includes but not limited to doped or non-doped PC60BM；The inorganic material with electron transport ability includes but not limited to doped or non-doped ZnO, TiO2、WO3、 NiO、MoO3、Fe2O3、SnO2In it is one or more；Preferably, the electron transfer layer 14 is ZnO；The electron-transport The thickness of layer 14 is 10 ~ 100 nm；Preferably, the thickness of the electron transfer layer is 20 ~ 50 nm；
The thickness of the quantum dot active layer 13 is 10 ~ 200 nm；Preferably, the thickness of the quantum dot active layer 13 is 50~100 nm。
The top electrode 15 be preferably metal electrode, the metal electrode may be selected from Al, Ag, Cu, Mo, Au or they Alloy；Preferably, the metal electrode is Au.The thickness of the metal electrode is 50 ~ 500 nm；Preferably, it is described The thickness of metal electrode is 100 ~ 200 nm.
Preferably, the quantum point probe is partial encapsulation, encapsulates or do not encapsulate entirely.
A kind of preparation method of quantum point probe as described above of the present invention, including step：
S1, one layer of hole injection layer is deposited on conductive substrates；
S2, one layer of quantum dot active layer is deposited on hole injection layer；The material of the quantum dot active layer is quanta point material, The quanta point material includes at least one quantum-dot structure unit arranged successively in radial directions, the quantum-dot structure Graded alloy component structure or in the radial direction level width consistent uniform of the unit for the variation of level width in the radial direction Component structure；
S3, one layer of electron transfer layer is deposited on quantum dot active layer；
S4, one layer of top electrode is deposited on the electron transport layer, obtains quantum point probe.
Further, it is further included after the step S1, before S2：
One layer of hole transmission layer is deposited on the hole injection layer.
Each layer（It is one or more in electron transfer layer, hole blocking layer, quantum dot active layer, hole transmission layer）It is heavy Chemical method or Physical may be used in product method, and wherein chemical method includes but not limited to chemical vapour deposition technique, continuous ionic layer Absorption with it is one or more in reaction method, anodizing, strike, coprecipitation；Physical includes but not limited to Spin-coating method, print process, knife coating, dip-coating method, infusion method, spray coating method, roll coating process, casting method, slit coating method, strip Rubbing method, thermal evaporation coating method, electron beam evaporation deposition method, magnetron sputtering method, multi-arc ion coating embrane method, physical vapour deposition (PVD) It is one or more in method, atomic layer deposition method, pulsed laser deposition；Preferably, the deposition method is spin-coating method, prints Brush method, thermal evaporation coating method.
The structure of quanta point material of the present invention is described in detail below：
Quanta point material provided by the present invention, including at least one quantum-dot structure list arranged successively in radial directions Member, the quantum-dot structure unit are graded alloy component structure or uniform alloy compositions structure.
That is in quanta point material provided by the invention, inside each quantum-dot structure unit from the inside to the outside radially It is the knot with alloy compositions in the range of one layer of monoatomic layer or one layer or more of monoatomic layer on direction in any position Structure, further, in the present invention, the quantum-dot structure unit is includes II races and VI races element.II races element includes But it is not limited to Zn, Cd, Hg, Cn etc.；VI races element includes but not limited to O, S, Se, Te, Po, Lv etc..Specifically, Mei Geliang The alloy compositions composition of son point structural unit is CdxZn1-xSeyS1-y, wherein 0≤x≤1,0≤y≤1, and during x with y differences It is 0 and be asynchronously 1；Should be noted the above situation is preferable case, for the quantum-dot structure list of graded alloy component structure For member, component is alloy compositions；And for the quantum-dot structure unit of homogeneous components structure, component can be Alloy compositions or non-alloyed component, but currently preferred is alloy compositions, i.e., and described homogeneous components structure is uniform Alloy compositions structure, it is further preferred that comprising II races and VI races element, subsequent embodiment of the present invention is with uniform alloy compositions knot It is illustrated for structure, it will be clear that can equally implement for unalloyed homogeneous components structure.
Further, the quantum-dot structure unit includes 2-20 layers of monoatomic layer or the quantum-dot structure unit packet Containing 1-10 layers of structure cell layer.Radial direction herein refers to the center outwardly direction from quanta point material, it is assumed for example that this hair Bright quanta point material is spherical or similar spherical structure, then the radial direction refers to the direction along radius, quanta point material Center（It is or internal）Refer to the center of its physical arrangement, the surface of quanta point material（It is or external）Refer to the table of its physical arrangement Face.
Specifically, as shown in Fig. 2, the present invention provides a kind of quanta point material with funnel type level structure, it is located at Quantum-dot structure unit level width inside the quanta point material is less than the quantum-dot structure being located at outside quanta point material Unit level width；That is, quanta point material provided by the invention is arranged successively in radial directions including at least one Quantum-dot structure unit, the quantum-dot structure unit is the wider graded alloy group of more outside level width in the radial direction Separation structure, and the energy level of the quantum-dot structure unit of graded alloy component structure adjacent in radial directions is continuous；Afterwards The structure of quanta point material shown in Fig. 2 is known as concrete structure 1 in continuous embodiment.Quanta point material in Fig. 2 is each adjacent The level width of quantum-dot structure unit has continuous structure, i.e., the level width of each adjacent quantum-dot structure unit has The characteristics of consecutive variations rather than mutation structure, that is to say, that the synthesis component of quantum dot be also with continuity, it is subsequent continuous Structural principle is identical.
Further, in radial directions in adjacent quantum-dot structure unit, by paracentral quantum-dot structure unit Level width is less than the level width of deep quantum-dot structure unit；That is, in the quanta point material, from The level width of center to face gradually broadens, so as to form the funnel type structure that opening becomes larger, opening therein It becomes larger and refers in level structure as shown in Figure 1, the energy level from quanta point material center to quanta point material surface is to connect Continuous.Meanwhile the quanta point material in the present invention, the energy level of each adjacent quantum-dot structure unit are continuous, that is, Saying the synthesis component of quantum dot also has the characteristic of consecutive variations, and this characteristic is more advantageous to realizing high luminous efficiency.
That is, the concrete structure 1 of the quanta point material be with from inside to outside radially it is continuous gradually Become the quantum-dot structure of alloy compositions；This quantum-dot structure has radially continuous from inside to outside become in constituent The characteristics of change；Correspondingly, energy level distribution on also on there are from inside to outside radially consecutive variations；This quantum Point structure in constituent and energy level distribution on consecutive variations the characteristics of, relative to quantum dot core and shell with clear and definite boundary Relationship, quanta point material of the invention not only contributes to realize more efficient luminous efficiency, while also can more meet semiconductor The comprehensive performance requirement of device and corresponding display technology to quanta point material, is a kind of suitable semiconductor devices and display technology Preferable quantum dot luminescent material.
Further, the alloy compositions such as Fig. 2 quanta point materials provided are：Cdx0 AZn1-x0 ASey0 AS1-y0 A, 0≤x0≤ 1,0≤y0≤1, and be 0 during x0 with y0 differences and be asynchronously 1.In quanta point material, the alloy compositions of A points are Cdx0 AZn1-x0 ASey0 AS1-y0 A, the alloy compositions of B points are Cdx0 BZn1-x0 BSey0 BS1-y0 B, wherein A points are relative to B points closer to amount Son point material center, and the composition of A points and B points meets：x0 A＞x0 B,y0 A＞y0 B.That is, for appointing in quanta point material Anticipate 2 point A points and B points, and A points relative to B points closer to quanta point material center, thenx0 A＞x0 B,y0 A＞y0 B, i.e. the Cd of A points Content is more than the Cd contents of B points, and the Zn contents of A points are less than the Zn contents of B points, and the Se contents of A points are more than the Se contents of B points, A points S contents be less than B points S contents.In this way, in the quanta point material, grading structure is just formd in radial directions, and It is more outside due in radial directions（I.e. far from quanta point material center）Then Cd and Se contents are lower, Zn and S contents are higher, So according to the characteristic of these types of element, level width will be wider.
In the quanta point material of follow-up difference concrete structure, if quantum-dot structure unit is more outside energy level in the radial direction The wider graded alloy component structure of width, then its alloy compositions be both preferably Cdx0Zn1-x0Sey0S1-y0, wherein, the alloy of A points Component is Cdx0 AZn1-x0 ASey0 AS1-y0 A, the alloy compositions of B points are Cdx0 BZn1-x0 BSey0 BS1-y0 B, wherein A points relative to B points more Close to quanta point material center, and the composition of A points and B points meets：x0 A>x0 B,y0 A >y0 B.If quantum-dot structure unit is radial direction side The upward narrower graded alloy component structure of more outside level width, then its alloy compositions be both preferably Cdx0Zn1-x0Sey0S1-y0, Wherein, the alloy compositions of C points are Cdx0 CZn1-x0 CSey0 CS1-y0 C, the alloy compositions of D points are Cdx0 DZn1-x0 DSey0 DS1-y0 D, wherein C It puts relative to D points closer to quanta point material center, and the composition of C points and D points meets：x0 C＜x0 D,y0 C＜y0 D.If quantum dot knot Structure unit is uniform alloy compositions structure（I.e. level width is consistent in the radial direction）, then its alloy compositions be both preferably Cdx0Zn1-x0Sey0S1-y0, wherein, the alloy compositions of E points are Cdx0 EZn1-x0 ESey0 ES1-y0 E, the alloy compositions of F points are Cdx0 FZn1-x0 FSey0 FS1-y0 F, wherein E points expire relative to F points closer to quanta point material center, and the composition of E points and F points Foot：x0 E=x0 F,y0 E=y0 F。
Further, as shown in figure 3, having inner alloy constituent the present invention also provides one kind, to correspond to level width little It is corresponded between level width and quantum-dot structure bosom and most external region containing at least one layer in exterior alloy constituent The quanta point material of the quantum-dot structure unit of uniform alloy compositions structure；That is, quanta point material provided by the invention The quantum-dot structure unit arranged successively in radial directions including at least three, wherein, at least three quantum-dot structure In unit, the quantum-dot structure unit positioned at center and surface is that the gradual change that more outside level width is wider in the radial direction is closed Golden component structure, a quantum-dot structure unit between center and the quantum-dot structure unit on surface are uniform alloy group Separation structure；And the energy level of the quantum-dot structure unit of adjacent graded alloy component structure is continuous in radial directions.Afterwards The structure of quanta point material shown in Fig. 3 is known as concrete structure 2 in continuous embodiment.
Specifically, as Fig. 3 provide quanta point material in, it is described between center and the quantum-dot structure unit on surface One layer of uniform alloy compositions structure quantum-dot structure unit alloy compositions be Cdx1Zn1-x1Sey1S1-y1, wherein 0≤x1≤ 1,0≤y1≤1, and be 0 during x1 with y1 differences and be asynchronously 1, and x1 and y1 is fixed value.Such as the alloy at certain point Component is Cd0.5Zn0.5Se0.5S0.5, and the alloy compositions at another point also should be Cd in the radial direction0.5Zn0.5Se0.5S0.5.Again Such as the homogeneous components of certain point are Cd in the quantum-dot structure unit of a certain uniform alloy compositions structure0.7Zn0.3S, and the amount The alloy compositions of another point also should be Cd in son point structural unit0.7Zn0.3S；In another example the amount of a certain uniform alloy compositions structure The homogeneous components of certain point are CdSe in son point structural unit, and the alloy compositions of another point also should in the quantum-dot structure unit For CdSe.
Further, as in the quanta point material of Fig. 3 offers, the quantum-dot structure unit positioned at center and surface is radially The wider graded alloy component structure of more outside level width on direction, and graded alloy component knot adjacent in radial directions The energy level of the quantum-dot structure unit of structure is continuous；I.e. in the quantum-dot structure unit with graded alloy component structure In, radially the corresponding level width of alloy constituent of upper any point is greater than adjacent and closer to quantum dot The corresponding level width of alloy constituent of structure centre another point.The quantum dot knot with graded alloy component structure Alloy compositions composition in structure unit is Cdx2Zn1-x2Sey2S1-y2, wherein 0≤x2≤1,0≤y2≤1, and x2 and y2 differences When be 0 and be asynchronously 1.Such as the alloy compositions of certain point are Cd0.5Zn0.5Se0.5S0.5, and the alloy compositions of another point are Cd0.3Zn0.7Se0.4S0.6。
That is, in the quanta point material provided in Fig. 3, other sections in addition to containing uniform alloy compositions section It is interior, along the corresponding level width of alloy constituent of quantum dot any point in the radial direction be greater than it is adjacent and closer to The corresponding level width of alloy constituent of the other points in quanta point material center.
Further, as shown in figure 4, the present invention also provides a kind of quantum of the full graded alloy component with quantum well structure Point material；That is, quanta point material provided by the invention includes two amounts point structural unit（A1 types and A2 types）, The wherein quantum-dot structure unit of A1 types is the wider graded alloy component structure of more outside level width in the radial direction, A2 The quantum-dot structure unit of type is the narrower graded alloy component structure of more outside level width in the radial direction, described two Quantum-dot structure unit is radially alternately distributed successively, and the amount of graded alloy component structure adjacent in radial directions The energy level of son point structural unit is continuous.That is, the quantum-dot structure cell distribution of the quanta point material can be： A1, A2, A1, A2, A1 ... or A2, A1, A2, A1, A2 ..., that is, the quantum-dot structure unit originated can be A1 types, Can also be A2 types.In the quantum-dot structure unit of A1 types, level width is more more outside wider, in the amount of A2 types In son point structural unit, level width is more more outside narrower, both level structures are like the form of wave is radially Side upwardly extends, and the structure of quanta point material shown in Fig. 4 is known as concrete structure 3 in subsequent embodiment.
Further, as shown in figure 5, the present invention also provides a kind of alloy compositions of the quantum well structure with energy level mutation Quanta point material, specifically, the quantum-dot structure unit are that the gradual change that more outside level width is wider in the radial direction is closed Golden component structure, and the level width of adjacent quantum-dot structure unit has mutation structure, i.e., each adjacent quantum dot knot The energy level of structure unit is discontinuous, i.e., the level width of each adjacent quantum-dot structure unit has the spy of discontinuous variation Point, that is, be mutated feature, that is to say, that the alloy compositions of quantum dot are also with mutability, and subsequent mutation structure principle is identical； The structure of quanta point material shown in Fig. 5 is known as concrete structure 4 in subsequent embodiment.
Specifically, the quanta point material described in Fig. 5 is arranged successively by way of mutation by multiple quantum-dot structure units Cloth is formed, these quantum-dot structure units are the graded alloy component structure that more outside level width is wider in the radial direction. Further, in the quanta point material, it is less than deep quantum by the level width of paracentral quantum-dot structure unit The level width of point structural unit.It is gradual from the level width of center to face that is, in the quanta point material It broadens, so as to the funnel type structure that the opening for forming interruption becomes larger, certainly, in the quanta point material, also not It is limited to aforesaid way, i.e., the level width of deep quantum-dot structure unit might be less that by paracentral quantum dot knot The level width of structure unit, in this structure, the level width of adjacent quantum-dot structure unit has the place being overlapping.
Further, as shown in fig. 6, having the alloy compositions of the quantum well structure of energy level mutation the present invention also provides another kind Quanta point material, specifically, the quantum-dot structure unit is the gradual change that more outside level width is narrower in the radial direction Alloy compositions structure, and the level width of adjacent quantum-dot structure unit has mutation structure, i.e., each adjacent quantum dot The energy level of structural unit is discontinuous, i.e., the level width of each adjacent quantum-dot structure unit has discontinuous variation Feature is mutated feature, that is to say, that the alloy compositions of quantum dot are also the subsequent mutation structure principle phase with mutability Together；The structure of quanta point material shown in Fig. 6 is known as concrete structure 5 in subsequent embodiment.
Specifically, the quanta point material described in Fig. 6 is arranged successively by way of mutation by multiple quantum-dot structure units Cloth is formed, these quantum-dot structure units are the graded alloy component structure that more outside level width is narrower in the radial direction. Further, in the quanta point material, it is more than deep quantum by the level width of paracentral quantum-dot structure unit The level width of point structural unit.It is gradual from the level width of center to face that is, in the quanta point material Narrow, so as to form the gradually smaller funnel type structure of the opening of interruption, certainly, in the quanta point material, also not It is limited to aforesaid way, i.e., the level width of deep quantum-dot structure unit can also be more than by paracentral quantum dot knot The level width of structure unit, in this structure, the level width of adjacent quantum-dot structure unit has the place being overlapping.
Further, as shown in fig. 7, the present invention also provides a kind of quanta point material, inside the quanta point material The level width of alloy constituent is become larger by center to outside, and quantum-dot structure most external region is uniform alloy group Point；Specifically, the quanta point material includes two amounts point structural unit（A3 types and A4 types）, wherein, A3 types Quantum-dot structure unit is the wider graded alloy component structure of more outside level width in the radial direction, the quantum dot of A4 types Structural unit is uniform alloy compositions structure, and the inside of the quanta point material includes one or more graded alloy group The quantum-dot structure unit of separation structure, and the quantum-dot structure unit of simplicity adjacent in radial directions and golden component structure Level width has continuous structure；The outside of the quanta point material includes one or more uniform alloy compositions structure Quantum-dot structure unit；The structure of quanta point material shown in Fig. 7 is known as concrete structure 6 in subsequent embodiment.
Specifically, in quanta point material as shown in Figure 7, quantum-dot structure unit is distributed as A3 ... A3A4 ... A4, The inside of i.e. described quanta point material is made of the quantum-dot structure unit of A3 types, the outside of the quanta point material be by The quantum-dot structure unit composition of A4 types, and the quantum-dot structure of the quantity of the quantum-dot structure unit of A3 types and A4 types The quantity of unit is all higher than being equal to 1.
Further, as shown in figure 8, the present invention also provides another quanta point material, inside the quanta point material Alloy constituent level width to be uniform, the level width of the alloy constituent outside the quantum dot by Center is to outside to become larger；Specifically, the quanta point material includes two amounts point structural unit（A5 types and A6 classes Type）, wherein, the quantum-dot structure unit of A5 types is uniform alloy compositions structure, and the quantum-dot structure unit of A6 types is diameter The wider graded alloy component structure of more outside level width on direction, the inside of the quanta point material include one or one The quantum-dot structure unit of a above uniform alloy compositions structure, the outside of the quanta point material include one or one with On graded alloy component structure quantum-dot structure unit, and the amount of graded alloy component structure adjacent in radial directions The energy level of son point structural unit is continuous；The structure of quanta point material shown in Fig. 8 is known as concrete structure in subsequent embodiment 7。
Specifically, in quanta point material as shown in Figure 8, monoatomic layer is distributed as A5 ... A5A6 ... A6 is that is, described The inside of quanta point material is made of the quantum-dot structure unit of A5 types, and the outside of the quanta point material is by A6 types Quantum-dot structure unit composition, and the quantum-dot structure unit of the quantity and A6 types of the quantum-dot structure unit of A5 types Quantity is all higher than being equal to 1.
Further, quantum-dot structure unit provided by the present invention includes 2-20 layers of monoatomic layer.Preferably, the amount Son point structural unit includes 2-5 monoatomic layer, and the preferred number of plies can ensure that quantum dot realizes good photoluminescence quantum yield And efficient charge injection efficiency.
Further, the quantum dot light emitting unit includes 1-10 layer crystals born of the same parents layer, preferably 2-5 layer crystals born of the same parents layer；The structure cell layer For minimum structural unit, i.e., its alloy compositions of each layer of structure cell layer are fixed, i.e., have the phase isomorphous in each structure cell layer Lattice parameter and element, the closed unit cell curved surface that each quantum-dot structure unit is the connection of structure cell layer and forms, adjacent cell layer Between level width have continuous structure or mutation structure.
The quanta point material of the present invention using the above structure, the photoluminescence quantum yield that can be realized ranging from 1% to 100%, Preferred photoluminescence quantum yield ranging from 30% to 100% can ensure the good of quantum dot in the range of preferred photoluminescence quantum yield Good application.
Wherein, the glow peak wave-length coverage of the quanta point material is 400 nanometers to 700 nanometers.
The quanta point material of the present invention using the above structure, the glow peak wave-length coverage that can be realized are 400 nanometers to 700 Nanometer, preferred glow peak wave-length coverage are 430 nanometers to 660 nanometers, and preferred quantum dot light emitting peak wave-length coverage can protect Card quanta point material realizes the photoluminescence quantum yield more than 30% within this range.
Further, in the present invention, the peak width at half height of the glow peak of the quanta point material is 12 nanometers to 80 nanometers.
Quanta point material of the present invention has the advantages that：First, help to reduce to the full extent not With the lattice tension between the quantum dot crystal of alloy compositions and alleviate lattice mismatch, so as to reduce the formation of boundary defect, carry The high luminous efficiency of quantum dot.Second, the level structure that quanta point material provided by the present invention is formed is more advantageous to pair Effective constraint of electron cloud in quantum dot greatly reduces diffusion probability of the electron cloud to quantum dot surface, so as to greatly inhibit The auger recombination loss of quantum dot radiationless transition, reduces quantum dot and flickers and improve quantum dot light emitting efficiency.Third, this hair The level structure that bright provided quanta point material is formed is more advantageous to the injection efficiency and efficiency of transmission of charge；It simultaneously can Effectively avoid the aggregation of charge and resulting Exciton quenching.4th, quanta point material provided by the present invention is formed Easily controllable diversity level structure can fully meet and coordination device in other functional layers level structure, with realize The matching of device entirety level structure.
The present invention also provides a kind of preparation method of quanta point material as described above, wherein, including step：
The first compound is synthesized in pre-position；
Second of compound, the first described compound and second of compound are synthesized on the surface of the first compound Alloy compositions are identical or different；
Make cation exchange reaction formation quanta point material, the amount occur between the first compound and second of chemical combination object Son point glow peak wavelength occur blue shift, red shift and it is constant in it is one or more.
Quantum dot SILAR synthetic methods incorporating quantum point one-step synthesis is generated quantum dot, tool by the preparation method of the present invention Body is using quantum dot SILAR synthetic method precise control amount sub- points successively grows and is formed gradually using quantum dot one-step synthesis Become component transition shell.Successively being formed two layers in radially pre-position has identical or different-alloy component compound By making between two layers of compound cation exchange reaction occurs for thin layer, so as to fulfill in the alloy compositions of pre-position point Cloth.Repeating above procedure can constantly realize that the alloy compositions in radial direction pre-position are distributed.
Described the first compound and second of compound can be binary or binary more than compound.
Further, when blue shift occurs in the glow peak wavelength of the quantum dot, illustrate that glow peak is moved to shortwave length direction, Level width broadens；When red shift occurs in the glow peak wavelength of the quantum dot, represent glow peak and moved to long wave direction, energy level Width narrows；When the glow peak wavelength of the quantum dot is constant, illustrate that level width is constant.
The cationic presoma of the first described compound and/or second of compound includes：The presoma of Zn, institute The presoma for stating Zn is zinc methide（dimethyl Zinc）, diethyl zinc（diethyl Zinc）, zinc acetate（Zinc acetate）, zinc acetylacetonate（Zinc acetylacetonate）, zinc iodide（Zinc iodide）, zinc bromide（Zinc bromide）, zinc chloride（Zinc chloride）, zinc fluoride（Zinc fluoride）, zinc carbonate（Zinc carbonate）、 Zinc cyanide（Zinc cyanide）, zinc nitrate（Zinc nitrate）, zinc oxide（Zinc oxide）, zinc peroxide（Zinc peroxide）, zinc perchlorate（Zinc perchlorate）, zinc sulfate（Zinc sulfate）, zinc oleate（Zinc oleate） Or zinc stearate（Zinc stearate）At least one of Deng, but not limited to this.
The cationic presoma of the first described compound and/or second of compound includes the presoma of Cd, institute The presoma for stating Cd is dimethyl cadmium（dimethyl cadmium）, diethyl cadmium（diethyl cadmium）, cadmium acetate （cadmium acetate）, acetylacetone,2,4-pentanedione cadmium（cadmium acetylacetonate）, cadmium iodide（cadmium iodide）、 Cadmium bromide（cadmium bromide）, caddy（cadmium chloride）, cadmium fluoride（cadmium fluoride）, carbon Sour cadmium（cadmium carbonate）, cadmium nitrate（cadmium nitrate）, cadmium oxide（cadmium oxide）, perchloric acid Cadmium（cadmium perchlorate）, cadmium phosphate（cadmium phosphide）, cadmium sulfate（cadmium sulfate）, oil Sour cadmium（cadmium oleate）Or cadmium stearate（cadmium stearate）At least one of Deng, but not limited to this.
The first change conjunction objects and/or the anion presoma of second of compound include the presoma of Se, example As Se with some organic matters arbitrarily combines formed compound, specifically Se-TOP (selenium- trioctylphosphine)、Se-TBP (selenium-tributylphosphine)、Se-TPP (selenium- triphenylphosphine)、Se-ODE (selenium-1-octadecene)、Se-OA (selenium-oleic acid)、Se-ODA (selenium-octadecylamine)、Se-TOA (selenium-trioctylamine)、Se- In ODPA (selenium-octadecylphosphonic acid) or Se-OLA (selenium-oleylamine) etc. At least one, but not limited to this.
The anion presoma of the first described compound and/or second of compound includes the presoma of S, such as S arbitrarily combines formed compound, specifically S-TOP (sulfur-trioctylphosphine), S- with some organic matters TBP(sulfur-tributylphosphine) 、S-TPP(sulfur-triphenylphosphine)、S-ODE (sulfur-1-octadecene) 、S-OA (sulfur-oleic acid)、S-ODA(sulfur-octadecylamine)、 S-TOA (sulfur-trioctylamine), S-ODPA (sulfur-octadecylphosphonic acid) or S-OLA At least one of (sulfur-oleylamine) etc., but not limited to this；The presoma of the S is alkyl hydrosulfide (alkyl Thiol), the alkyl hydrosulfide is hexyl mercaptan (hexanethiol), spicy thioalcohol (octanethiol), decyl mercaptan (decanethiol), lauryl mercaptan (dodecanethiol), hexadecyl mercaptan (hexadecanethiol) or mercaptos At least one of propyl silane (mercaptopropylsilane) etc., but not limited to this.
The anion presoma of the first described compound and/or second of compound further includes the presoma of Te, The presoma of the Te is Te-TOP, Te-TBP, Te-TPP, Te-ODE, Te-OA, Te-ODA, Te-TOA, Te-ODPA or Te- At least one of OLA.
In the preparation process in accordance with the present invention, the condition that cation exchange reaction occurs is to carry out heating reaction, such as heat Temperature is between 100 DEG C to 400 DEG C, between preferred heating temperature is 150 DEG C to 380 DEG C.Heating time 2s to for 24 hours it Between, preferred heating time is 5min between 4h.
Above-mentioned cation precursor and anion presoma can form to determine selection according to final quanta point material One or more therein：Such as it needs to synthesize CdxZn1-xSeyS1-yQuanta point material when, then need the presoma of Cd, Zn Presoma, the presoma of Se, S presoma；If desired for synthesis CdxZn1-xDuring the quanta point material of S, then the forerunner of Cd is needed Body, the presoma of Zn, S presoma；If desired for synthesis CdxZn1-xDuring the quanta point material of Se, then presoma, the Zn of Cd are needed Presoma, Se presoma.
Heating temperature is higher, and the rate of cation exchange reaction is faster, the thickness range of cation exchange and exchange degree Also it is bigger, but thickness and extent and scope can progressively reach the degree of relative saturation；Similar, heating time is longer, and cation is handed over The thickness range and exchange degree changed is also bigger, but thickness and extent and scope can also progressively reach the degree of relative saturation.Sun from The thickness range and degree that son exchanges directly determine formed graded alloy component distribution.Cation exchange is formed gradually Become alloy compositions distribution also to be determined by the binary or the thickness of multi-element compounds nanocrystal that are respectively formed simultaneously.
When forming each layer compound, the molar ratio of cationic presoma and anion presoma can be 100:1 to 1: 50（The specially molar feed ratio of cation and anion）, such as when forming first layer compound, cationic presoma with The molar ratio of anion presoma is 100:1 to 1:50；When forming second layer compound, before cationic presoma and anion The molar ratio for driving body is 100:1 to 1:50, preferred ratio is 20:1 to 1:10, preferred cation presoma with before anion Driving the molar ratio of body can ensure reaction rate in easily controllable range.
By the quanta point material prepared by above-mentioned preparation method, glow peak wave-length coverage is received for 400 nanometers to 700 Rice, preferred glow peak wave-length coverage are 430 nanometers to 660 nanometers, and preferred quantum dot light emitting peak wave-length coverage can ensure Quantum dot realizes the photoluminescence quantum yield more than 30% within this range.
Quanta point material prepared by method made above, photoluminescence quantum yield ranging from 1% to 100% are preferred to shine Quantum yield ranging from 30% to 100% can ensure the applications well of quantum dot in the range of preferred photoluminescence quantum yield.
Further, in the present invention, the peak width at half height of the glow peak of the quanta point material is 12 nanometers to 80 nanometers.
Other than the quanta point material of the present invention is prepared according to above-mentioned preparation method, the present invention also provides another such as The preparation method of the upper quanta point material, including step：
Pre-position adds in one or more kinds of cationic presomas in radial directions；It adds in simultaneously under certain condition One or more kinds of anion presomas, makes cationic presoma react forming quantum dot material with anion presoma Material, and the glow peak wavelength of the quanta point material occur during the reaction blue shift, red shift and it is constant in one kind or several Kind, it is distributed so as to fulfill in the graded alloy component of pre-position.
The difference that method and former approach are sent out for such side is that former is successively to form two layers of compound, then Cation exchange reaction occurs, is distributed so as to fulfill alloy compositions needed for the present invention, and later approach is directly controlled pre- It positions the place of putting and adds in the required synthesis cationic presoma of alloy compositions and anion presoma, carry out reaction and forming quantum dot material Material, is distributed so as to fulfill alloy compositions needed for the present invention.For later approach, reaction principle is the high cation of reactivity Presoma and anion presoma first react, and occur after the low cationic presoma of reactivity and anion presoma anti- Should, and during the reaction, cation exchange reaction occurs for different cations, so as to fulfill alloy compositions needed for the present invention Distribution.It has been described in detail in preceding method as the type of cationic presoma and anion presoma.As for reaction temperature, instead Between seasonable and proportioning etc. can the quanta point material of synthesis according to needed for specific it is different and different, with aforementioned former side Method is substantially the same, and is subsequently illustrated with specific embodiment.
Embodiment 1：Preparation based on CdZnSeS/CdZnSeS quantum dots
First the presoma of the presoma of cationic Cd, the presoma of cation Zn, the presoma of anion Se and anion S are noted Enter into reaction system, form CdyZn1-ySebS1-bLayer（Wherein 0≤y≤1,0≤b≤1）；Continue the forerunner of cationic Cd Body, the presoma of cation Zn, the presoma of anion Se and the presoma of anion S are injected into reaction system, above-mentioned CdyZn1-ySebS1-bLayer surface forms CdzZn1-zSecS1-cLayer（Wherein 0≤z≤1, and z is not equal to y, 0≤c≤1）；Certain Heating temperature and the reaction conditions such as heating time under, ectonexine nanocrystal occurs（I.e. above-mentioned two layers of compound）Middle Cd and Zn The exchange of ion；The probability migrated due to the limited and more remote migration distance of migration distance of cation with regard to smaller, It can be in CdyZn1-ySebS1-bLayer and CdzZn1-zSecS1-cThe near interface of layer forms the graded alloy component of Cd contents and Zn contents Distribution, i.e. CdxZn1-xSeaS1-a, wherein 0≤x≤1,0≤a≤1.
Embodiment 2：Preparation based on CdZnS/CdZnS quantum dots
First the presoma of the presoma of cationic Cd, the presoma of cation Zn and anion S is injected into reaction system, It is initially formed CdyZn1-yS layers（Wherein 0≤y≤1）；Continue by the presoma of cationic Cd, cation Zn presoma and it is cloudy from The presoma of sub- S is injected into reaction system, can be in above-mentioned CdyZn1-yS layer surfaces form CdzZn1-zS layers（Wherein 0≤z≤1, And z is not equal to y）；Under the reaction conditions such as certain heating temperature and heating time, ectonexine nanocrystal occurs（It is i.e. above-mentioned Two layers of compound）The exchange of middle Cd and Zn ions；Since the limited and more remote migration distance of the migration distance of cation is moved The probability of shifting, therefore can be in Cd with regard to smalleryZn1-yS layers and CdzZn1-zS layers of near interface forms Cd contents and Zn contents gradually Become alloy compositions distribution, i.e. CdxZn1-xS, wherein 0≤x≤1.
Embodiment 3：Preparation based on CdZnSe/CdZnSe quantum dots
First the presoma of the presoma of cationic Cd, the presoma of cation Zn and anion Se is injected into reaction system It is initially formed CdyZn1-ySe layers（Wherein 0≤y≤1）；Continue the presoma and the moon of the presoma of cationic Cd, cation Zn The presoma of ion Se is injected into reaction system, can be in above-mentioned CdyZn1-ySe layer surfaces form CdzZn1-zSe layers（Wherein 0≤z ≤ 1, and z is not equal to y）；Under the reaction conditions such as certain heating temperature and heating time, Cd in ectonexine nanocrystal occurs With the exchange of Zn ions；The probability migrated due to the limited and more remote migration distance of migration distance of cation with regard to smaller, It therefore can be in CdyZn1-ySe layers and CdzZn1-zSe layers of near interface forms the graded alloy component point of Cd contents and Zn contents Cloth, i.e. CdxZn1-xSe, wherein 0≤x≤1.
Embodiment 4：Preparation based on CdS/ZnS quantum dots
First the presoma of the presoma of cationic Cd and anion S is injected into reaction system, is initially formed CdS layer；Continuing will The presoma of cationic Zn and the presoma of anion S are injected into reaction system, can form ZnS layers on above-mentioned CdS layer surface； Under the reaction conditions such as certain heating temperature and heating time, the Zn cations of outer layer can gradual inner layer migration, and and Cd Cation exchange reaction occurs for cation, i.e. Cd ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to cation The probability that migrates of the limited and more remote migration distance of migration distance with regard to smaller, therefore can be in CdS layer and ZnS layers of interface Be formed about Cd contents it is radially outward gradually decrease, the radially outward graded alloy component gradually increased point of Zn contents Cloth, i.e. CdxZn1-xS, wherein 0≤x≤1 and x is from inside to outside（Radial direction）It is 0 from 1 monotone decreasing.
Embodiment 5：Preparation based on CdSe/ZnSe quantum dots
First the presoma of the presoma of cationic Cd and anion Se is injected into reaction system and is initially formed CdSe layers；Continuing will The presoma of cationic Zn and the presoma of anion Se are injected into reaction system, can form ZnSe in above-mentioned CdSe layer surfaces Layer；Under the reaction conditions such as certain heating temperature and heating time, the Zn cations of outer layer can gradual inner layer migration, and with Cation exchange reaction occurs for Cd cations, i.e. Cd ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to sun from The probability that the limited and more remote migration distance of migration distance of son migrates, therefore can be in CdSe layers and ZnSe layer with regard to smaller Near interface formed Cd contents it is radially outward gradually decrease, the radially outward graded alloy group gradually increased of Zn contents Distribution, i.e. CdxZn1-xSe, wherein 0≤x≤1 and x is from inside to outside（Radial direction）It is 0 from 1 monotone decreasing.
Embodiment 6：Preparation based on CdSeS/ZnSeS quantum dots
First the presoma of the presoma of cationic Cd, the presoma of anion Se and anion S is injected into reaction system It is initially formed CdSebS1-bLayer（Wherein 0≤b≤1）；Continue by the presoma of cationic Zn, anion Se presoma and it is cloudy from The presoma of sub- S is injected into reaction system, can be in above-mentioned CdSebS1-bLayer surface forms ZnSecS1-cLayer（Wherein 0≤c≤1）； Under the reaction conditions such as certain heating temperature and heating time, the Zn cations of outer layer can gradual inner layer migration, and and Cd Cation exchange reaction occurs for cation, i.e. Cd ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to cation The probability that migrates of the limited and more remote migration distance of migration distance with regard to smaller, therefore can be in CdSebS1-bLayer with ZnSecS1-cThe near interface of layer formed Cd contents it is radially outward gradually decrease, Zn contents are radially outward gradually increases Graded alloy component distribution, i.e. CdxZn1-xSeaS1-a, wherein 0≤x≤1 and x is from inside to outside（Radial direction）From 1 monotone decreasing It is 0,0≤a≤1.
Embodiment 7：Preparation based on ZnS/CdS quantum dots
First the presoma of the presoma of cationic Zn and anion S is injected into reaction system and is initially formed ZnS layers；Continuing will be positive The presoma of ion Cd and the presoma of anion S are injected into reaction system, can form CdS layer in above-mentioned ZnS layer surfaces； Under the reaction conditions such as certain heating temperature and heating time, the Cd cations of outer layer can gradual inner layer migration, and with Zn sun Cation exchange reaction occurs for ion, i.e. Zn ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to cation The probability that the limited and more remote migration distance of migration distance migrates, therefore can be attached with the interface of CdS layer at ZnS layers with regard to smaller It is near formed Zn contents it is radially outward gradually decrease, the radially outward graded alloy component point gradually increased of Cd contents Cloth, i.e. CdxZn1-xS, wherein 0≤x≤1 and x is from inside to outside（Radial direction）It is 1 from 0 monotonic increase.
Embodiment 8：Preparation based on ZnSe/CdSe quantum dots
First the presoma of the presoma of cationic Zn and anion Se is injected into reaction system and is initially formed ZnSe layer；Continuing will The presoma of cationic Cd and the presoma of anion Se are injected into reaction system, can form CdSe on above-mentioned ZnSe layer surface Layer；Under the reaction conditions such as certain heating temperature and heating time, the Cd cations of outer layer can gradual inner layer migration, and with Cation exchange reaction occurs for Zn cations, i.e. Zn ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to sun from The probability that the limited and more remote migration distance of migration distance of son migrates, therefore can be in ZnSe layer and CdSe layers with regard to smaller Near interface formed Zn contents it is radially outward gradually decrease, the radially outward graded alloy group gradually increased of Cd contents Distribution, i.e. CdxZn1-xSe, wherein 0≤x≤1 and x is from inside to outside（Radial direction）It is 1 from 0 monotonic increase.
Embodiment 9：Preparation based on ZnSeS/CdSeS quantum dots
First the presoma of the presoma of cationic Zn, the presoma of anion Se and anion S is injected into reaction system It is initially formed ZnSebS1-bLayer（Wherein 0≤b≤1）；Continue by the presoma of cationic Cd, anion Se presoma and it is cloudy from The presoma of sub- S is injected into reaction system, can form CdSe in above-mentioned ZnSebS1-b layer surfacescS1-cLayer（Wherein 0≤c≤ 1）；Under the reaction conditions such as certain heating temperature and heating time, the Cd cations of outer layer can gradual inner layer migration, and with Cation exchange reaction occurs for Zn cations, i.e. Zn ions outer layers migrate, and the exchange of Cd and Zn ions has occurred；Due to sun from The probability that the limited and more remote migration distance of migration distance of son migrates, therefore can be in ZnSe with regard to smallerbS1-bLayer with CdSecS1-cThe near interface of layer formed Zn contents it is radially outward gradually decrease, Cd contents are radially outward gradually increases Graded alloy component distribution, i.e. CdxZn1-xSeaS1-a, wherein 0≤x≤1 and x are from inside to outside 1 from 0 monotonic increase, 0≤a≤ 1。
Embodiment 10：The preparation of blue quantum dot with concrete structure 1
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted Enter into reaction system, after reacting 10 min, by trioctylphosphine sulfide presoma and cadmium oleate presoma respectively with 3 mL/h and The rate of 10 mL/h is added dropwise in reaction system.After reaction, after reaction solution is cooled to room temperature, with toluene and nothing Product is dissolved, precipitated by water methanol repeatedly, is then centrifuged for purifying, and obtains the blue quantum dot with concrete structure 1（CdxZn1- xS）.
Embodiment 11：The preparation of green quantum dot with concrete structure 1
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.4 mmol cadmium oxides（CdO）, 8 mmol zinc acetates [Zn (acet)2], 10 ML oleic acid（Oleic acid）It is placed in 100 mL three-necked flasks, 60 min of vacuum outgas is carried out at 80 DEG C.Then it is cut It changes under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）, 4 mmol sulphur powders（Sulfur powder）It is dissolved in the three of 4 mL Octyl group phosphine（Trio ctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 2 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three Octyl group phosphine presoma is rapidly injected in reaction system, first generates CdxZn1-xSeyS1-y, after reacting 10 min, by the vulcanization of 2mL Tri octyl phosphine presoma is added dropwise to the rate of 8 mL/h in reaction system, until presoma has injected.After reaction, After reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification obtains having tool The green quantum dot of body structure 1（CdxZn1-xSeyS1-y/CdzZn1-zS）, prepared green quantum is represented before "/" herein The composition of the inside of point, "/" then represents the composition outside prepared green quantum dot below, and "/" representative is not It is apparent boundary, but the structure of gradual change from inside to outside, this quantum dot representation method meaning subsequently occurred are identical.
Embodiment 12：The preparation of red quantum dot with concrete structure 1
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2], 14 mL oleic acid（Oleic acid）It is placed in 100 mL three-necked flasks, 60 min of vacuum outgas is carried out at 80 DEG C.Then by it It switches under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4 mL（Trioctylphosphine）In, it obtains To selenizing tri octyl phosphine presoma.
By 0.2 mmol selenium powders（Selenium powder）, 0.6 mmol sulphur powders（Sulfur powder）It is dissolved in 2 mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, selenizing tri octyl phosphine presoma is fast Speed is injected into reaction system, first generates CdxZn1-xSe, it is after reacting 10 min, selenizing tri octyl phosphine-vulcanization three of 2mL is pungent Base phosphine presoma is added dropwise to the rate of 4 mL/h in reaction system.After reaction, after reaction solution is cooled to room temperature, Product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification obtains the red fluorescence quantum with concrete structure 1 Point（CdxZn1-xSeyS1-y/CdzZn1-zS）.
Embodiment 13：The influence that cadmium oleate charge velocity synthesizes the blue quantum dot with concrete structure 1
On the basis of embodiment 10, the graded of quantum dot component can be regulated and controled by the charge velocity for adjusting cadmium oleate Slope, so as to influence its level structure, the final regulation and control realized to quantum dot light emitting wavelength.
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, at 80 DEG C Carry out 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted Enter into reaction system, first generate CdxZn1-xS, react 10 min after, by trioctylphosphine sulfide presoma with 3 mL/h rates by It is added dropwise in reaction system, while cadmium oleate presoma is added dropwise to different charge velocities in reaction system.Instead After answering, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification obtains To the blue quantum dot with level structure 1（CdxZn1-xS/CdyZn1-yS）.
Based on identical quantum dot center（Alloy quantum dot glow peak 447nm）And the injection speed of different cadmium oleate presomas Under rate, quantum dot light emitting wavelength tuning control is listed as follows：
Embodiment 14：The influence that cadmium oleate injection rate synthesizes the blue quantum dot with concrete structure 1
On the basis of embodiment 10 and embodiment 13, by adjusting the injection rate of cadmium oleate presoma, quantum dot can be regulated and controled Ingredient graded section, so as to influence the variation of its level structure, the final tune realized to quantum dot light emitting wavelength Control.Based on identical quantum dot center（Alloy quantum dot glow peak 447nm）And the injection rate of different cadmium oleate presomas（It is identical 1 mmol/h under charge velocity）Under rate, quantum dot light emitting wavelength tuning control is listed as follows.
Embodiment 15：The preparation of blue quantum dot with concrete structure 2
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL Oleic acid（Oleic acid）With 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted Enter into reaction system, first generate CdxZn1-xTemperature of reaction system after reacting 10 min, is down to 280 DEG C, then by 2mL by S Trioctylphosphine sulfide presoma and 6mL cadmium oleates presoma reaction is injected into the rate of 3 mL/h and 10mL/h simultaneously respectively In system.After injecting 40 min, temperature of reaction system is warming up to 310 DEG C, by 1mL trioctylphosphine sulfides presoma with 3 mL/h Rate be injected into reaction system, after reaction, after reaction solution is cooled to room temperature, with toluene and absolute methanol by product It dissolves, precipitate repeatedly, centrifugation purification obtains the blue quantum dot of concrete structure 2.
Embodiment 16：The preparation of green quantum dot with concrete structure 2
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.4 mmol cadmium oxides（CdO）, 8 mmol zinc acetates [Zn (acet) 2], 10 ML oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）Be placed in 100 mL three-necked flasks, at 80 DEG C into 60 min of row vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）, 4 mmol sulphur powders（Sulfur powder）It is dissolved in the three of 4mL Octyl group phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
By 2mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 2mL（Trioctylphosphine）In, it obtains To trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three Octyl group phosphine presoma is rapidly injected in reaction system, first generates CdxZn1-xSeyS1-y, after reacting 10 min, by reaction system temperature Degree is down to 280 DEG C, then by the trioctylphosphine sulfide presoma of 1.2mL and 6mL cadmium oleates presoma respectively with 2 mL/h and The rate of 10mL/h is injected into reaction system, until presoma has injected.Temperature of reaction system is warming up to 310 DEG C, by 0.8 ML trioctylphosphine sulfides presoma is injected into the rate of 2 mL/h in reaction system.After reaction, treat that reaction solution is cooled to After room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification obtains the amount of green color with concrete structure 2 Sub- point.
Embodiment 17：The preparation of red quantum dot with concrete structure 2
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2], 14 mL oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, at 80 DEG C Carry out 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4mL（Trioctylphosphine）In, it obtains To selenizing tri octyl phosphine presoma.
By 0.2 mmol selenium powders（Selenium powder）, 0.6 mmol sulphur powders（Sulfur powder）It is dissolved in 2mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
By 0.3 mmol cadmium oxides（CdO）, 0.3mL oleic acid（Oleic acid）With 2.7 mL octadecylenes（1- Octadecene）It is placed in 50 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, selenizing tri octyl phosphine presoma is fast Speed is injected into reaction system, first generates CdxZn1-xTemperature of reaction system after reacting 10 min, is down to 280 DEG C, then by Se By 1mL selenizings tri octyl phosphine-trioctylphosphine sulfide presoma and 3mL cadmium oleates presoma respectively with the speed of 2 mL/h and 6 mL/h Rate is injected into reaction system.Temperature of reaction system is warming up to 310 DEG C, before 1mL selenizings tri octyl phosphine-trioctylphosphine sulfide Body is driven to be injected into reaction system with the rate of 4 mL/h.After reaction, after reaction solution is cooled to room temperature, with toluene and nothing Product is dissolved, precipitated by water methanol repeatedly, and centrifugation purification obtains the red quantum dot with concrete structure 2.
Embodiment 18：The preparation of blue quantum dot with concrete structure 3
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.2 mmol selenium powders（Selenium powder）It is dissolved in the tri octyl phosphine of 1 mL （Trioctylphosphine）In, obtain selenizing tri octyl phosphine presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted Enter into reaction system, first generate CdxZn1-xS, after reacting 10 min, by cadmium oleate presoma and trioctylphosphine sulfide presoma It is continuously injected into 20 min to reaction system with the rate of 0.6 mmol/h, 4 mmol/h respectively.Then by cadmium oleate presoma, Trioctylphosphine sulfide presoma and selenizing tri octyl phosphine presoma are respectively with 0.4 mmol/h, 0.6 mmol/h and 0.2 mmol/h Rate be continuously injected into 1 h to reaction system.After reaction, after reaction solution is cooled to room temperature, with toluene and without water beetle Product is dissolved, precipitated by alcohol repeatedly, and centrifugation purification is obtained with Quantum Well（Concrete structure 3）Blue quantum dot (CdZnS/CdZnS/CdZnSeS3)。
Embodiment 19：The preparation of green quantum dot with concrete structure 3
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.4 mmol cadmium oxides（CdO）, 6 mmol zinc acetates [Zn (acet)2], 10 ML oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）Be placed in 100 mL three-necked flasks, at 80 DEG C into 60 min of row vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 0.4 mmol selenium powders（Selenium powder）, 4 mmol sulphur powders（Sulfur powder）It is dissolved in 4 mL's Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 1.
By 0.1 mmol selenium powders（Selenium powder）, 0.3 mmol sulphur powders（Sulfur powder）It is dissolved in 2 mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 2.
By 0.8 mmol sulphur powders（Sulfur powder）, 0.8 mmol selenium powders（Selenium powder）It is dissolved in 3 mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 3.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three Octyl group phosphine presoma 1 is rapidly injected in reaction system, first generates CdxZn1-xSeyS1-y, after reacting 5 min, by the selenizing of 2mL Tri octyl phosphine-trioctylphosphine sulfide presoma 2 is added dropwise to the rate of 6 mL/h in reaction system.Then, by the selenium of 3mL Change the cadmium oleate presoma of tri octyl phosphine-trioctylphosphine sulfide presoma 3 and 6mL respectively with 3 mL/h and 6 mL/h rates after It is continuous to be added dropwise in reaction system.After reaction, after reaction solution is cooled to room temperature, with toluene and absolute methanol by product It dissolves, precipitate repeatedly, centrifugation purification obtains the green quantum dot (CdZn with concrete structure 33SeS3/Zn4SeS3/ Cd3Zn5Se4S4)。
Embodiment 20：The preparation of red quantum dot with concrete structure 3
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2], 14 mL oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, at 80 DEG C Carry out 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4 mL（Trioctylphosphine）In, it obtains To selenizing tri octyl phosphine presoma.
By 0.2 mmol selenium powders（Selenium powder）, 0.6 mmol sulphur powders（Sulfur powder）It is dissolved in 2 mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
By 0.9 mmol cadmium oxides（CdO）, 0.9 mL oleic acid（Oleic acid）With 8.1 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, selenizing tri octyl phosphine presoma is fast Speed is injected into reaction system, first generates CdxZn1-xSe, it is after reacting 10 min, selenizing tri octyl phosphine-vulcanization three of 2 mL is pungent Base phosphine presoma is added dropwise to the rate of 2 mL/h in reaction system.When being injected into 30 min, before the cadmium oleate of 3 mL Body is driven to be added dropwise in reaction system with 6 mL/h rates simultaneously.After reaction, after reaction solution is cooled to room temperature, first is used Product is dissolved, precipitated by benzene and absolute methanol repeatedly, and centrifugation purification obtains the red quantum dot with concrete structure 3 （CdxZn1-xSe/ZnSeyS1-y/CdzZn1-zSeS）.
Embodiment 21：The preparation of blue quantum dot with concrete structure 4
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.2mmol selenium powders（Selenium powder）It is dissolved in the tri octyl phosphine of 1mL（Trioctylphosphine） In, obtain selenizing tri octyl phosphine presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted Enter into reaction system, first generate CdxZn1-xS, after reacting 10 min, by cadmium oleate presoma and selenizing tri octyl phosphine forerunner Body is continuously injected into the rate of 0.6 mmol/h, 0.6 mmol/h in 20 min to reaction system respectively.It then will be before cadmium oleate It drives body and trioctylphosphine sulfide presoma is continuously injected into 1h to reaction system with the rate of 0.4 mmol/h and 6 mmol/h respectively In.After reaction, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation carries It is pure, it obtains with Quantum Well（Concrete structure 4）Blue quantum dot（CdZnS/CdZnSe/CdZnS）.
Embodiment 22：The preparation of green quantum dot with concrete structure 4
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.4 mmol selenium powders（Selenium powder）It is dissolved in the tri octyl phosphine of 2 mL （Trioctylphosphine）In, obtain selenizing tri octyl phosphine presoma.
By 0.8 mmol cadmium oxides（CdO）, 1.2 mL oleic acid（Oleic acid）With 4.8 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted Enter into reaction system, first generate CdxZn1-xS, after reacting 10 min, by cadmium oleate presoma and selenizing tri octyl phosphine presoma It is continuously injected into 40 min to reaction system with the rate of 0.6 mmol/h, 0.6 mmol/h respectively.Then by cadmium oleate forerunner Body and trioctylphosphine sulfide presoma are continuously injected into 1 h to reaction system with the rate of 0.4 mmol/h and 6 mmol/h respectively In.After reaction, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation carries It is pure, it obtains with Quantum Well（Concrete structure 4）Green quantum dot（CdZnS/CdZnSe/CdZnS）.
Embodiment 23：The preparation of red quantum dot with concrete structure 4
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2], 14 mL oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, at 80 DEG C Carry out 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 1.5 mmol selenium powders（Selenium powder）, 1.75 mmol sulphur powders（Sulfur powder）It is dissolved in 3mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 1.
By 1 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 2mL（Trioctylphosphine）In, it obtains To selenizing tri octyl phosphine presoma.
By 0.2 mmol selenium powders（Selenium powder）, 0.8 mmol sulphur powders（Sulfur powder）It is dissolved in 2mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 2.
By 3 mmol cadmium oxides（CdO）, 3mL oleic acid（Oleic acid）With 6 mL octadecylenes（1-Octadecene）It is placed in In 100 mL three-necked flasks, it is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent cadmium oleate presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three Octyl group phosphine presoma 1 is injected into reaction system, first generates CdxZn1-xSe, after reacting 10 min, by the selenizing trioctylphosphine of 2 mL The cadmium oleate presoma of phosphine presoma and 3mL are added dropwise to the rate of 4 mL/h and 6 mL/h in reaction system respectively.Note When entering to 30 min, by the cadmium oleate presoma of selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 2 of 2mL and 3mL respectively with 2 mL/h and 3 mL/h rates are added dropwise in reaction system.After reaction, after reaction solution is cooled to room temperature, toluene is used Product is dissolved repeatedly with absolute methanol, is precipitated, centrifugation purification obtains the red quantum dot of concrete structure 4（CdxZn1-xSe/ CdZnSe/CdzZn1-zSeS）.
Embodiment 24：The preparation of blue quantum dot with concrete structure 5
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet)2], 8 mL Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 1 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted Enter into reaction system, first generate CdxZn1-xS, after reacting 10 min, by 3 mL trioctylphosphine sulfides presomas with 3 mL/h's Rate is continuously injected into 1h to reaction system, when trioctylphosphine sulfide presoma injects 20 min, by 2 mL cadmium oleate forerunners Body is injected into 6 mL/h in reaction system, when trioctylphosphine sulfide presoma injects 40 min, by 4 mL cadmium oleate forerunners Body is injected into 12 mL/h in reaction system.After reaction, after reaction solution is cooled to room temperature, with toluene and absolute methanol Product is dissolved repeatedly, is precipitated, centrifugation purification is obtained with Quantum Well（Concrete structure 5）Blue quantum dot （CdZnS/ZnS/CdZnS）.
Embodiment 25：The preparation of green quantum dot with concrete structure 5
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.4 mmol cadmium oxides（CdO）, 6 mmol zinc acetates [Zn (acet)2], 10 ML oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）Be placed in 100 mL three-necked flasks, at 80 DEG C into 60 min of row vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 0.4 mmol selenium powders（Selenium powder）, 4 mmol sulphur powders（Sulfur powder）It is dissolved in 4mL's Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma 1.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three Octyl group phosphine presoma is rapidly injected in reaction system, first generates CdxZn1-xSeyS1-y, after reacting 10 min, 3 mL are vulcanized three Octyl group phosphine presoma is continuously injected into the rate of 3 mL/h in 1h to reaction system, injects 20 in trioctylphosphine sulfide presoma During min, 2 mL cadmium oleates presomas are injected into 6 mL/h in reaction system, inject 40 in trioctylphosphine sulfide presoma During min, 4 mL cadmium oleates presomas are injected into 12 mL/h in reaction system.After reaction, treat that reaction solution is cooled to room Product with toluene and absolute methanol is dissolved, precipitated by Wen Hou repeatedly, and centrifugation purification is obtained with Quantum Well（Specifically Structure 5）Green quantum dot（CdZnSeS/ZnS/CdZnS）.
Embodiment 26：The preparation of red quantum dot with concrete structure 5
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2], 14 mL oleic acid（Oleic acid）With 20 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, at 80 DEG C Carry out 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4mL（Trioctylphosphine）In, it obtains To selenizing tri octyl phosphine presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, selenizing tri octyl phosphine presoma is fast Speed is injected into reaction system, first generates CdxZn1-xSe, after reacting 10 min, by trioctylphosphine sulfide presoma with 6 mmol/ The rate of h is continuously injected into 1h to reaction system, when S-TOP injects 20 min, by 0.2 mmol cadmium oleate presomas with 0.6 Mmol/h is injected into reaction system, when S-TOP injects 40 min, by 0.4 mmol cadmium oleates presoma with 1.2 mmol/h It is injected into reaction system.After reaction, it is with toluene and absolute methanol that product is repeatedly molten after reaction solution is cooled to room temperature Solution, precipitation, centrifugation purification, obtain with Quantum Well（Concrete structure 5）Red quantum dot（CdZnSe/ZnS/ CdZnS）.
Embodiment 27：The preparation of blue quantum dot with concrete structure 6
It is prepared by cadmium oleate and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet) 2], 8 mL Oleic acid（Oleic acid）And 15 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is carried out at 80 DEG C 60 min of vacuum outgas.Then it switches it under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1- Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 min for 250 DEG C under nitrogen atmosphere, obtains transparent oil Sour cadmium presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, sulphur octadecylene presoma is quickly noted Enter into reaction system, first generate CdxZn1-xS, after reacting 10 min, by trioctylphosphine sulfide presoma and cadmium oleate presoma It is added dropwise in reaction system with the rate of 6mmol/h and 0.6 mmol/h respectively.After 30 min, temperature of reaction system is dropped To 280 DEG C, by remaining trioctylphosphine sulfide presoma and cadmium oleate presoma respectively with the speed of 6mmol/h and 0.6 mmol/h Rate is added dropwise in reaction system.After reaction, after reaction solution is cooled to room temperature, with toluene and absolute methanol by product It dissolves, precipitate repeatedly, centrifugation purification obtains the blue quantum dot with concrete structure 6（CdxZn1-xS）.
Embodiment 28：The preparation of green quantum dot with concrete structure 6
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.4 mmol cadmium oxides（CdO）, 8 mmol zinc acetates [Zn (acet)2], 10 ML oleic acid（Oleic acid）It is placed in 100 mL three-necked flasks, 60 min of vacuum outgas is carried out at 80 DEG C.Then it is cut It changes under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）, 4 mmol sulphur powders（Sulfur powder）It is dissolved in the three of 4mL Octyl group phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
By 2mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 2mL（Trioctylphosphine）In, it obtains To trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, by selenizing tri octyl phosphine-vulcanization three Octyl group phosphine presoma is rapidly injected in reaction system, first generates CdxZn1-xSeyS1-y, after reacting 10 min, by reaction system Temperature is down to 280 DEG C, and trioctylphosphine sulfide presoma is added dropwise to the rate of 4 mL/h in reaction system.Reaction terminates Afterwards, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification is had The green quantum dot of concrete structure 6（CdxZn1-xSeyS1-y/ZnS）.
Embodiment 29：The preparation of red quantum dot with concrete structure 6
It is prepared by cadmium oleate and oleic acid zinc precursor：By 0.8 mmol cadmium oxides（CdO）, 12 mmol zinc acetates [Zn (acet)2], 14 mL oleic acid（Oleic acid）It is placed in 100 mL three-necked flasks, 60 min of vacuum outgas is carried out at 80 DEG C.Then by it It switches under nitrogen atmosphere, and in preservation at this temperature in case for use.
By 2 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4mL（Trioctylphosphine）In, it obtains To selenizing tri octyl phosphine presoma.
By 0.2 mmol selenium powders（Selenium powder）, 0.6 mmol sulphur powders（Sulfur powder）It is dissolved in 2mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate and oleic acid zinc precursor are warming up to 310 DEG C, selenizing tri octyl phosphine presoma is fast Speed is injected into reaction system, first generates CdxZn1-xTemperature of reaction system after reacting 10 min, is down to 280 DEG C, by selenium by Se Change tri octyl phosphine-trioctylphosphine sulfide presoma to be added dropwise in reaction system with the rate of 4 mL/h.After reaction, it treats After reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification obtains having specific The red quantum dot of structure 6（CdxZn1-xSe/ZnSeS）.
Embodiment 30：The preparation of green quantum dot with concrete structure 7
It is prepared by the first presoma of cadmium oleate：By 1 mmol cadmium oxides（CdO）, 1 mL oleic acid（Oleic acid）With 5 mL octadecylenes （1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.Then it switches it to Into under nitrogen atmosphere, and in preservation at this temperature in case for use.
It is prepared by the second presoma of cadmium oleate：By 0.6 mmol cadmium oxides（CdO）, 0.6 mL oleic acid（Oleic acid）With 5.4 mL octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, is heated to reflux 120 for 250 DEG C under nitrogen atmosphere Mins obtains transparent the second presoma of cadmium oleate.
It is prepared by oleic acid zinc precursor：By 9 mmol zinc acetates [Zn (acet)2], 7 mL oleic acid（Oleic acid）And 10 ML octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.Then It switches it under nitrogen atmosphere, and is heated to reflux preserving in case for use in lower 250 DEG C of nitrogen atmosphere.
By 2 mmol sulphur powders（Sulfur powder）It is dissolved in the octadecylene of 3 mL（1-Octadecene）In, obtain sulphur Octadecylene presoma.
By 6 mmol sulphur powders（Sulfur powder）It is dissolved in the tri octyl phosphine of 3 mL（Trioctylphosphine）In, Obtain trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, the first presoma of cadmium oleate is warming up to 310 DEG C, sulphur octadecylene presoma is rapidly injected Into reaction system, CdS is quickly generated, after reacting 10 mins, oleic acid zinc precursor is all injected into reaction system, then by 3 The trioctylphosphine sulfide presoma of mL and 6 the second presomas of mL cadmium oleates are noted simultaneously with the rate of 3 mL/h and 10 mL/h respectively Enter into reaction system.
After reaction, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, Centrifugation purification, obtains the blue quantum dot with Quantum Well.
Embodiment 31：The preparation of green quantum dot with concrete structure 7
It is prepared by cadmium oleate presoma：By 0.4 mmol cadmium oxides（CdO）, 1 mL oleic acid（Oleic acid）With 5 mL octadecylenes （1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.Then by it in nitrogen Atmosphere is enclosed lower 250 DEG C and is heated to reflux, and in preservation at this temperature in case for use.
By 0.4 mmol selenium powders（Selenium powder）, it is dissolved in the tri octyl phosphine of 4 mL （Trioctylphosphine）In, obtain selenizing tri octyl phosphine.
It is prepared by oleic acid zinc precursor：By 8 mmol zinc acetates [Zn (acet)2], 9 mL oleic acid（Oleic acid）With 15 ML octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.In nitrogen Atmosphere encloses lower 250 DEG C and is heated to reflux 120 mins, obtains transparent oleic acid zinc precursor.
By 2 mmol sulphur powders（Sulfur powder）With 1.6 mmol selenium powders（Selenium powder）It is dissolved in 2 mL Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate presoma is warming up to 310 DEG C, selenizing tri octyl phosphine presoma is rapidly injected Into reaction system, CdSe is quickly generated, after reacting 5 mins, oleic acid zinc precursor is all injected into reaction system, by 2 Selenizing tri octyl phosphine-trioctylphosphine sulfide presoma of mL is added dropwise to the rate of 2 mL/h in reaction system, until before Body is driven to have injected.After reaction, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is sunk It forms sediment, centrifugation purification obtains the green fluorescence quantum dot with Quantum Well.
Embodiment 32：The preparation of red quantum dot with concrete structure 7
It is prepared by cadmium oleate presoma：By 0.8 mmol cadmium oxides（CdO）, 4 mL oleic acid（Oleic acid）With 10 mL octadecylenes （1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.Then by it in nitrogen Atmosphere is enclosed lower 250 DEG C and is heated to reflux, and in preservation at this temperature in case for use.
It is prepared by oleic acid zinc precursor：12 mmol zinc acetates [Zn (acet)2], 10 mL oleic acid（Oleic acid）With 10 ML octadecylenes（1-Octadecene）It is placed in 100 mL three-necked flasks, 60 mins of vacuum outgas is carried out at 80 DEG C.
By 0.8 mmol selenium powders（Selenium powder）In the tri octyl phosphine of 4 mL（Trioctylphosphine）In, Obtain selenizing tri octyl phosphine presoma.
By 1 mmol selenium powders（Selenium powder）, 0.6 mmol sulphur powders（Sulfur powder）It is dissolved in 2 mL's Tri octyl phosphine（Trioctylphosphine）In, obtain selenizing tri octyl phosphine-trioctylphosphine sulfide presoma.
Under nitrogen atmosphere, cadmium oleate presoma is warming up to 310 DEG C, selenizing tri octyl phosphine presoma is rapidly injected Into reaction system, CdSe is quickly generated, after reacting 10 mins, oleic acid zinc precursor is all injected into reaction system, it will Selenizing tri octyl phosphine-trioctylphosphine sulfide presoma of 2 mL is added dropwise to the rate of 4 mL/h in reaction system.Reaction After, after reaction solution is cooled to room temperature, product is dissolved repeatedly with toluene and absolute methanol, is precipitated, centrifugation purification obtains Red fluorescence quantum dot with Quantum Well.
Embodiment 33 is as shown in figure 9, a kind of quantum point probe, preparation process include the following steps：
(1) ITO is prepared on a substrate 20（Hearth electrode 21）；
(2) one layer of PEDOT of spin coating on ITO:PSS layer（Hole injection layer 22）, thickness is 30 nm；
（3）, in the PEDOT:One layer poly-TPD layers of spin coating in PSS layer（Hole transmission layer 23）, thickness 60nm.
(4) one layer of quanta point material of spin coating obtains quantum dot active layer 24, thickness 80nm on poly-TPD layers；Its In quanta point material be the quantum dot of any one in previous embodiment；
(5) the spin coating layer of ZnO layer on the quantum dot active layer（Electron transfer layer 25）, thickness 30nm.
(6) the Au electrodes that a layer thickness is 150 nm are deposited in ZnO layer（Top electrode 26）, obtain quantum point probe.
It should be understood that the application of the present invention is not limited to the above, it for those of ordinary skills, can To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention Protect range.

Claims (15)

1. a kind of quantum point probe, which is characterized in that include successively：Conductive substrates, hole injection layer, quantum dot active layer, Electron transfer layer and top electrode；The material of the quantum dot active layer is quanta point material, including at least one in radial direction side The quantum-dot structure unit arranged successively upwards, the quantum-dot structure unit are closed for the gradual change of radial direction level width variation The consistent homogeneous components structure of golden component structure or in the radial direction level width.
2. quantum point probe according to claim 1, which is characterized in that the hole injection layer and quantum dot active layer Between be provided with one layer of hole transmission layer.
3. quantum point probe according to claim 1 or 2, which is characterized in that the quantum-dot structure unit is diameter The wider graded alloy component structure of more outside level width on direction, and graded alloy component adjacent in radial directions The energy level of the quantum-dot structure unit of structure is continuous.
4. quantum point probe according to claim 1 or 2, which is characterized in that the quanta point material includes at least three A quantum-dot structure unit arranged successively in radial directions, wherein, in at least three quantum-dot structures unit, it is located at The quantum-dot structure unit on center and surface is the graded alloy component structure that more outside level width is wider in the radial direction, And the energy level of the quantum-dot structure unit of adjacent graded alloy component structure is continuous in radial directions；Positioned at center and A quantum-dot structure unit between the quantum-dot structure unit on surface is homogeneous components structure.
5. quantum point probe according to claim 1 or 2, which is characterized in that the quanta point material includes two types The quantum-dot structure unit of type, the quantum-dot structure unit of one of which type are wider for more outside level width in the radial direction Graded alloy component structure, another type of quantum-dot structure unit is narrower for more outside level width in the radial direction Graded alloy component structure, the quantum-dot structure unit of described two types are radially alternately distributed successively, and radially The energy level of the quantum-dot structure unit of adjacent graded alloy component structure is continuous on direction.
6. quantum point probe according to claim 1 or 2, which is characterized in that the quantum-dot structure unit is diameter The wider graded alloy component structure of more outside level width on direction, and the energy level of adjacent quantum-dot structure unit is not Continuously.
7. quantum point probe according to claim 1 or 2, which is characterized in that the quantum-dot structure unit is diameter The narrower graded alloy component structure of more outside level width on direction, and the energy level of adjacent quantum-dot structure unit is not Continuously.
8. quantum point probe according to claim 1 or 2, which is characterized in that the quanta point material includes two amounts Son point structural unit, one of which quantum-dot structure unit is the wider graded alloy group of more outside level width in the radial direction Separation structure, another quantum-dot structure unit are homogeneous components structure, and the inside of the quanta point material includes one or one The quantum-dot structure unit of above graded alloy component structure, and graded alloy component structure adjacent in radial directions The energy level of quantum-dot structure unit is continuous；The outside of the quanta point material includes one or more homogeneous components The quantum-dot structure unit of structure.
9. quantum point probe according to claim 1 or 2, which is characterized in that the quanta point material includes two amounts Son point structural unit, one of which quantum-dot structure unit are homogeneous components structure, and another quantum-dot structure unit is radially The wider graded alloy component structure of more outside level width on direction, the inside of the quanta point material include one or one The quantum-dot structure unit of above homogeneous components structure, the outside of the quanta point material include it is one or more gradually Become the quantum-dot structure unit of alloy compositions structure, and the quantum dot knot of graded alloy component structure adjacent in radial directions The energy level of structure unit is continuous.
10. quantum point probe according to claim 1 or 2, which is characterized in that the quantum-dot structure unit be comprising The graded alloy component structure or uniform alloy compositions structure of II races and VI races element.
11. quantum point probe according to claim 1 or 2, which is characterized in that the quantum-dot structure unit includes 2- 20 layers of monoatomic layer or the quantum-dot structure unit include 1-10 layers of structure cell layer.
12. quantum point probe according to claim 1 or 2, which is characterized in that the luminous spike of the quanta point material It is ranging from 400 nanometers to 700 nanometers long.
13. quantum point probe according to claim 1 or 2, which is characterized in that the glow peak of the quanta point material Peak width at half height is 12 nanometers to 80 nanometers.
14. a kind of preparation method of quantum point probe as described in claim 1, which is characterized in that including step：
A, one layer of hole injection layer is deposited on conductive substrates；
B, one layer of quantum dot active layer is deposited on hole injection layer；The material of the quantum dot active layer is quanta point material, The quanta point material includes at least one quantum-dot structure unit arranged successively in radial directions, the quantum-dot structure Graded alloy component structure or in the radial direction level width consistent uniform of the unit for the variation of level width in the radial direction Component structure；
C, one layer of electron transfer layer is deposited on quantum dot active layer；
D, one layer of top electrode is deposited on the electron transport layer, obtains quantum point probe.
15. the preparation method of quantum point probe according to claim 14, which is characterized in that after the step A, It is further included before B：
One layer of hole transmission layer is deposited on the hole injection layer.
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CN109904278A (en) * 2018-12-18 2019-06-18 杭州电子科技大学 A kind of photodetector and preparation method
CN110702744A (en) * 2019-10-17 2020-01-17 山东交通学院 Special treatment device and sensing system for ship tail gas
CN113054049A (en) * 2019-12-28 2021-06-29 Tcl集团股份有限公司 Quantum dot photoelectric detector and preparation method thereof

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CN104736234A (en) * 2012-08-30 2015-06-24 应用纳米技术中枢(Can)有限公司 Method for producing core/shell nanoparticles and core/shell nanoparticles
CN105493295A (en) * 2013-08-29 2016-04-13 佛罗里达大学研究基金会有限公司 Air stable infrared photodetectors from solution-processed inorganic semiconductors

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CN101842460A (en) * 2007-10-30 2010-09-22 伊斯曼柯达公司 Device containing non-blinking quantum dots
CN104736234A (en) * 2012-08-30 2015-06-24 应用纳米技术中枢(Can)有限公司 Method for producing core/shell nanoparticles and core/shell nanoparticles
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CN109904278A (en) * 2018-12-18 2019-06-18 杭州电子科技大学 A kind of photodetector and preparation method
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