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CN108264901A - Luminescent material, preparation method and semiconductor devices with funnel type level structure - Google Patents

Luminescent material, preparation method and semiconductor devices with funnel type level structure Download PDF

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CN108264901A
CN108264901A CN201611255825.3A CN201611255825A CN108264901A CN 108264901 A CN108264901 A CN 108264901A CN 201611255825 A CN201611255825 A CN 201611255825A CN 108264901 A CN108264901 A CN 108264901A
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luminescent material
quantum
presoma
zinc
cadmium
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CN108264901B (en
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刘政
杨行
杨一行
钱磊
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TCL Corp
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • C09K11/562—Chalcogenides
    • C09K11/565—Chalcogenides with zinc cadmium
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots

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Abstract

The present invention discloses the luminescent material with funnel type level structure, preparation method and semiconductor devices, wherein, the luminescent material includes N number of quantum-dot structure unit arranged successively in radial directions, wherein N >=2；The quantum-dot structure unit includes A1 and A2 types, and the A1 types are the wider graded alloy component structure of more outside level width in the radial direction；The A2 types are the consistent homogeneous components structure of level width in the radial direction；The inside of the luminescent material is made of the quantum-dot structure unit of at least one layer of A1 types, and the outside of the luminescent material is made of the quantum-dot structure unit of at least one layer of A2 types；In radial directions in adjacent quantum-dot structure unit, the level width of the quantum-dot structure unit far from luminescent material center is not more than close to the level width of the quantum-dot structure unit at luminescent material center；And the energy level of the quantum-dot structure unit of adjacent graded alloy component structure is continuous.

Description

Luminescent material, preparation method and semiconductor devices with funnel type level structure
Technical field
The present invention relates to field of light emitting materials more particularly to there is the luminescent material of funnel type level structure, preparation method And semiconductor devices.
Background technology
Quantum dot is a kind of special material for being limited in nanometer scale in three dimensions, this significant Quantum confined effect causes quantum dot to be provided with many unique nanometer properties：Launch wavelength is continuously adjusted, emission wavelength is narrow, is inhaled Receive spectral width, luminous intensity height, fluorescence lifetime length and good biocompatibility etc..These features cause quantum dot to be shown in tablet Show, the fields such as solid-state lighting, photovoltaic solar, biomarker are respectively provided with the prospect of being widely applied.It especially should in FPD With aspect, the quanta point electroluminescent diode component based on quanta point material（Quantum dot light-emitting Diodes, QLED）Characteristic and optimization by means of CdS quantum dots, in display image quality, device performance, manufacture cost Etc. shown huge potentiality.Although the performance of QLED devices in all respects is continuously available promotion in recent years no matter It is also to have phase with the requirement of commercial application in device efficiency or in the basic devices performance parameter such as device job stability When gap, this also hinders the development and application of quanta point electroluminescent display technology significantly.In addition, it is not limited only to QLED devices Part, in other areas, quanta point material are also gradually paid attention to relative to the characteristic of traditional material, such as photo luminescent devices, Solar cell, display device, photodetector, bioprobe and device for non-linear optical etc., below only with QLED devices It is illustrated for part.
Although quantum dot has been studied and developed more than 30 years as a kind of nano material of classics, quantum is utilized The superior luminescence characteristics of point simultaneously apply the search time in QLED devices and corresponding display technology as luminescent material It is also very short；Therefore the R and D of the QLED devices of the overwhelming majority are all based on the quantum dot for having classical architecture system at present Material, the standard of screening and the optimization of corresponding quanta point material is also substantially from the luminescent properties such as quantum of quantum dot itself The luminous peak width of point, solution quantum yield etc. set out.More than quantum dot is directly applied in QLED device architectures so as to obtain Corresponding device performance result.
But the photoelectric device system of QLED devices and corresponding display technology as a set of complexity, there is all various factors It can influence the performance of device.List is from the quanta point material as core emitting layer material, the quantum dot performance of required tradeoff Index will be much more complex.
First, quantum dot is existing in the form of quantum dot light emitting layer solid film in QLED devices, therefore quantum Originally obtained every luminescent properties parameter can show apparent difference to point material after solid film is formed in the solution： Such as glow peak wavelength has different degrees of red shift in solid film（It is moved to long wavelength）, shine peak width can become larger, Quantum yield has different degrees of reduction, that is to say, that the superior luminescence performance of quanta point material in the solution can not be complete It is inherited into the quantum dot solid film of QLED devices.Therefore in the structure and synthesizing formula for designing and optimizing quanta point material When, the hair of the luminescent properties optimization and quanta point material of quanta point material itself under solid film state need to be considered simultaneously Optical property, which is inherited, to be maximized.
Secondly, the luminous of quanta point material is realized by electroexcitation in QLED devices, i.e., respectively from QLED Anode and cathodal closing the injection hole of device and electronics, hole and electronics are existed by the transmission of corresponding function layer in QLED devices After quantum dot light emitting layer is compound, emitted by way of radiation transistion photon realize shine.From above procedure as can be seen that amount It is to influence the efficiency of radiation transistion in the above process that son, which puts the luminescent properties of itself such as luminous efficiency, and QLED devices is whole Body luminous efficiency can also simultaneously by hole in the above process and electronics in quanta point material charge injection and efficiency of transmission, Relative charge balance in quanta point material of hole and electronics, the recombination region of hole and electronics in quanta point material etc. It influences.Therefore when designing and optimizing the fine nanometer nuclear shell nano-structure of structure especially quantum dot of quanta point material, weight is also needed Point considers that quantum dot forms the later electric property of solid film：Such as the charge of quantum dot injects and conductive performance, quantum dot Fine band structure, quantum dot exciton lifetime etc..
Finally, it is contemplated that QLED devices and corresponding display technology future will pass through the solution rule of great production cost advantage If prepared by ink-jet printing, therefore the design of material of quantum dot and exploitation need to consider the processing performance of quantum dot solution, Such as the dispersible dissolubility of quantum dot solution or marking ink, colloidal stability, it is printed as film property etc..Meanwhile quantum dot material The exploitation of material will also be cooperateed with the whole preparation process flow and requirement of other functional layer materials of QLED devices and device.
In short, traditional only being designed from the quantum-dot structure for promoting quantum dot itself luminescent properties consideration is can not to expire Sufficient QLED devices and corresponding display technology are various in optical property, electric property, processing performance etc. for quanta point material Composite request.The requirement for QLED devices and corresponding display technology is needed, to the fine nucleocapsid knot of quantum dot light emitting material Structure, component, energy level etc. carry out customized.
Due to the high surface atom ratio of quantum dot, not with surface ligand（Ligand）Form non-covalent bond（Dangling bond）Atom will exist with surface defect state, this surface defect state will cause the transition of non-radiative pathway so that The photoluminescence quantum yield of quantum dot is substantially lowered.To solve this problem, it can grow and include in former quantum dot superficies The semiconductor shell of another semi-conducting material forms the nucleocapsid of quantum dot（core-shell）Structure, can the amount of significantly improving The luminescent properties of son point, while increase the stability of quantum dot.
The quanta point material that can be applied to the exploitation of high-performance QLED devices is mainly the quantum dot of nucleocapsid, core and shell Fixed and nucleocapsid has clear and definite boundary, such as quantum dot (the J. Phys. with CdSe/ZnS nucleocapsids to ingredient respectively Chem., 1996,100 (2), 468-471), there is quantum dot (the J. Am. Chem. of CdSe/CdS nucleocapsids Soc. 1997,119, (30), 7019-7029), the quantum dot with CdS/ZnS nucleocapsids, with CdS/CdSe/CdS The quantum dot (7,919,012 B2 of Patent US) of core+multilayer shell structurre has CdSe/CdS/ZnS cores+multilayer shell Quantum dot (J. Phys. Chem. B, 2004,108 (49), 18826-18831) of structure etc..In these nucleocapsids Quantum dot in, usually the constituent of core and shell is fixed and different, and is usually by a kind of cation and one The binary compound system of kind anion composition.In this configuration, since the growth of core and shell is independently to carry out respectively, because Boundary between this core and shell is clear and definite, i.e., core and shell can be distinguished.The exploitation of this nuclear shell structure quantum point improves original Luminous quantum efficiency, monodispersity and the quantum dot stability of first single component quantum dot.
Although the quantum dot part of nucleocapsid described above improves quantum dot performance, from mentality of designing or From prioritization scheme or from the aspect of the luminous efficiency based on promotion quantum dot itself, luminescent properties need to be improved, In addition other aspect particular/special requirements of semiconductor devices for quanta point material are not considered yet.
Therefore, above-mentioned technology 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 the luminous materials with funnel type level structure Material, preparation method and semiconductor devices, it is intended to solve that existing luminescent material its luminescent properties are to be improved, can not meet and partly lead The problem of requirement of the body device for luminescent material.
Technical scheme is as follows：
A kind of luminescent material with funnel type level structure, wherein, the luminescent material include it is N number of in radial directions successively The quantum-dot structure unit of arrangement, wherein N >=2；
The quantum-dot structure unit includes A1 and A2 types, and the A1 types are wider for more outside level width in the radial direction Graded alloy component structure；The A2 types are the consistent homogeneous components structure of level width in the radial direction；
The inside of the luminescent material is made of the quantum-dot structure unit of at least one layer of A1 types, the outside of the luminescent material It is made of the quantum-dot structure unit of at least one layer of A2 types；
In radial directions in adjacent quantum-dot structure unit, close to the energy level of the quantum-dot structure unit at luminescent material center Width is not more than the level width of the quantum-dot structure unit far from luminescent material center；And adjacent graded alloy component structure The energy level of quantum-dot structure unit be continuous.
The luminescent material, wherein, the quantum-dot structure unit of the A1 types is comprising II races and VI races element Graded alloy component structure, the quantum-dot structure unit of the A2 types is the uniform alloy compositions comprising II races and VI races element Structure.
The luminescent material, wherein, the alloy compositions of the quantum-dot structure unit of the A1 types are Cdx0Zn1- x0Sey0S1-y0, wherein 0≤x0≤1,0≤y0≤1, and it is 0 during x0 with y0 differences and is asynchronously 1.
The luminescent material, wherein, the alloy compositions composition of the quantum-dot structure unit of the A2 types is Cdx1Zn1-x1Sey1S1-y1, wherein 0≤x1≤1,0≤y1≤1, and it is 0 during x1 with y1 differences and is asynchronously 1, and x1 and y1 It is fixed value in the quantum-dot structure unit of corresponding A2 types.
The luminescent material, wherein, in the quantum-dot structure unit of the A1 types, 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 hair Luminescent material center, and the composition of A points and B points meets：x0 A>x0 B,y0 A>y0 B。
The luminescent material, wherein, the quantum-dot structure unit includes 2-20 layers of monoatomic layer or the amount Son point structural unit includes 1-10 layers of structure cell layer.
The luminescent material, wherein, two of adjacent quantum-dot structure unit intersection are single former in radial directions Two of continuous alloy compositions structure or quantum-dot structure unit intersection adjacent in radial directions are formed between sublayer Continuous alloy compositions structure is formed between structure cell layer.
The luminescent material, wherein, the glow peak wave-length coverage of the luminescent material is 400 nanometers to 700 nanometers.
The luminescent material, wherein, the peak width at half height of the glow peak of the luminescent material is 12 nanometers to 80 nanometers.
A kind of preparation method of luminescent 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 luminescent material occurs between the first compound and second of chemical combination object, it is described to shine First there is blue shift in the glow peak wavelength of material, then constant.
The preparation method of the luminescent material, wherein, the first described compound and/or second of compound Cationic presoma includes the presoma of Zn, and the presoma of the Zn is zinc methide, diethyl zinc, zinc acetate, acetylacetone,2,4-pentanedione Zinc, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, zinc nitrate, zinc oxide, zinc peroxide, zinc perchlorate, At least one of zinc sulfate, zinc oleate or zinc stearate.
The preparation method of the luminescent material, wherein, the first described compound and/or second of compound Cationic presoma further includes the presoma of Cd, and the presoma of the Cd is dimethyl cadmium, diethyl cadmium, cadmium acetate, levulinic Ketone cadmium, cadmium iodide, cadmium bromide, caddy, cadmium fluoride, cadmium carbonate, cadmium nitrate, cadmium oxide, cadmium perchlorate, cadmium phosphate, cadmium sulfate, At least one of cadmium oleate or cadmium stearate.
The preparation method of the luminescent material, wherein, the first described compound and/or second of compound Anion presoma includes the presoma of Se, the presoma of the Se is Se-TOP, Se-TBP, Se-TPP, Se-ODE, Se-OA, At least one of Se-ODA, Se-TOA, Se-ODPA or Se-OLA.
The preparation method of the luminescent material, wherein, the first described compound and/or second of compound Anion presoma further includes the presoma of S, and the presoma of the S is S-TOP, S-TBP, S-TPP, S-ODE, S-OA, S- At least one of ODA, S-TOA, S-ODPA, S-OLA or alkyl hydrosulfide.
The preparation method of the luminescent material, wherein, the first described compound and/or second compound it is cloudy from Sub- presoma further includes the presoma of Te, the presoma of the Te is Te-TOP, Te-TBP, Te-TPP, Te-ODE, Te-OA, At least one of Te-ODA, Te-TOA, Te-ODPA or Te-OLA.
The preparation method of the luminescent material, wherein, make the first compound and second of chemical combination in a heated condition Cation exchange reaction occurs between object.
The preparation method of the luminescent material, wherein, heating temperature is between 100 DEG C to 400 DEG C.
The preparation method of the luminescent material, wherein, heating time is in 2s between for 24 hours.
The preparation method of the luminescent material, wherein, when synthesizing the first compound, cationic presoma with it is cloudy from The molar ratio of sub- presoma is 100:1 to 1:Between 50.
The preparation method of the luminescent material, wherein, when synthesizing second of compound, cationic presoma with it is cloudy from The molar ratio of sub- presoma is 100:1 to 1:Between 50.
A kind of semiconductor devices, wherein, including as above any one of them luminescent material.
The semiconductor devices, wherein, the semiconductor devices is electroluminescent device, photo luminescent devices, the sun Can be in battery, display device, photodetector, bioprobe and device for non-linear optical any one.
Advantageous effect：The present invention provides a kind of luminous materials with graded alloy component from inside to outside radially Material, not only realizes more efficient quanta point material luminous efficiency, while also can more meet semiconductor devices and corresponding display Comprehensive performance requirement of the technology to luminescent material, is a kind of suitable semiconductor devices and the desired illumination material of display technology.
Description of the drawings
Fig. 1 is a kind of level structure curve of the luminescent material preferred embodiment with funnel type level structure of the present invention.
Fig. 2 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 13.
Fig. 3 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 14.
Fig. 4 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 15.
Fig. 5 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 16.
Fig. 6 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 17.
Fig. 7 is the structure diagram of light emitting diode with quantum dots in the embodiment of the present invention 18.
Specific embodiment
The present invention provides a kind of luminescent material, preparation method and semiconductor devices with funnel type level structure, to make The purpose of the present invention, technical solution and effect are clearer, clear and definite, and the present invention is described in more detail below.It should be appreciated that The specific embodiments described herein are merely illustrative of the present invention, is not intended to limit the present invention.
Luminescent material provided by the present invention with funnel type level structure, wherein, the luminescent material include it is N number of The quantum-dot structure unit arranged successively in the radial direction, wherein N >=2；
The quantum-dot structure unit includes A1 and A2 types, and the A1 types are wider for more outside level width in the radial direction Graded alloy component structure；The A2 types are the consistent homogeneous components structure of level width in the radial direction；Diameter herein Refer to the center outwardly direction from luminescent material to direction, it is assumed for example that luminescent material of the invention is spherical or similar spherical Structure, then the radial direction refers to the direction along radius, and the center of luminescent material refers to the center of its physical arrangement, and shine material The surface of material refers to the surface of its physical arrangement.
The inside of the luminescent material is made of the quantum-dot structure unit of at least one layer of A1 types, the luminescent material Outside is made of the quantum-dot structure unit of at least one layer of A2 types；
In radial directions in adjacent quantum-dot structure unit, close to the energy level of the quantum-dot structure unit at luminescent material center Width is not more than the level width of the quantum-dot structure unit far from luminescent material center；And adjacent graded alloy component structure The energy level of quantum-dot structure unit be continuous, that is to say, that when the inside of the luminescent material includes at least two layers of A1 type Quantum-dot structure unit when, then the energy level of the quantum-dot structure unit of the adjacent A1 types is continuous；It is i.e. of the invention In each adjacent graded alloy component structure quantum-dot structure unit level width have the characteristics that consecutive variations rather than Mutation structure, that is to say, that the inside synthesis component of luminescent material has continuity, and this characteristic is more advantageous to realizing high hair Light efficiency.
Luminescent material in the present invention belongs to the quanta point material of Quantum Well, level structure such as Fig. 1 institutes Show.In the i.e. described luminescent material, quantum-dot structure unit is distributed as A1 ... A1A2 ... A2, i.e., described luminescent material it is interior Portion is made of the quantum-dot structure unit of A1 types, and the outside of the luminescent material is the quantum-dot structure unit by A2 types Composition, and the quantity of the quantum-dot structure unit of the quantity and A2 types of the quantum-dot structure unit of A1 types is all higher than being equal to 1；
In the quantum-dot structure unit of A1 types, level width is more more outside wider, in the quantum-dot structure list of A2 types In member, level width is uniform；In radial directions in adjacent quantum-dot structure unit, by paracentral quantum dot knot The level width of structure unit is not more than the level width of deep quantum-dot structure unit；And adjacent quantum dot structural unit Level width have continuous structure.The level structure of Fig. 1 is referred to as Quantum Well in a particular embodiment.
Further, the quantum-dot structure unit of the A1 types is the graded alloy component knot comprising II races and VI races element Structure, the quantum-dot structure unit of the A2 types is the uniform alloy compositions structure comprising II races and VI races element.The II races Element includes but not limited to Zn, Cd, Hg, Cn etc..VI races element includes but not limited to O, S, Se, Te, Po, Lv etc..It needs Bright is that the above situation is preferable case, and for the quantum-dot structure unit of graded alloy component structure, 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, more excellent Choosing, comprising II races and VI races element, subsequent embodiment of the present invention is illustrated by taking uniform alloy compositions structure as an example, but Can equally it implement clearly for unalloyed homogeneous components structure.
Further, the alloy compositions of the quantum-dot structure unit of the A1 types are Cdx0Zn1-x0Sey0S1-y0, wherein 0≤ X0≤1,0≤y0≤1, and be 0 during x0 with y0 differences and be asynchronously 1.Such as the alloy compositions at a certain position are Cd0.5Zn0.5Se0.5S0.5, and the alloy compositions of another position are Cd0.3Zn0.7Se0.4S0.6。
The luminescent material, wherein, the alloy compositions composition of the quantum-dot structure unit of the A2 types is Cdx1Zn1-x1Sey1S1-y1, wherein 0≤x1≤1,0≤y1≤1, and it is 0 during x1 with y1 differences and is asynchronously 1, and x1 and y1 It is fixed value in the quantum-dot structure unit of corresponding A2 types.Such as the alloy compositions at a certain position are Cd0.5Zn0.5Se0.5S0.5, and the alloy compositions of another position also should be Cd0.5Zn0.5Se0.5S0.5。
Further, in the quantum-dot structure unit of the A1 types, 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 in luminescent material The heart, and the composition of A points and B points meets：x0 A>x0 B,y0 A>y0 B.That is, for arbitrary in A1 type quantum-dot structure units 2 point A points and B points, and A points relative to B points closer to luminescent material center, thenx0 A>x0 B,y0 A >y0 B, i.e. the Cd contents of A points More than the Cd contents of B points, 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, the S of A points Content is less than the S contents of B points.In this way, in A1 type quantum-dot structure units, graded junction is just formd in radial directions Structure, and due in radial directions, it is more outside（That is the center far from luminescent material）Then Cd and Se contents are lower, and Zn and S contain Amount is higher, then according to the characteristic of these types of element, level width will be wider.
Further, the quantum-dot structure unit includes 2-20 layers of monoatomic layer.That is, each quantum-dot structure unit All include 2-20 layers of monoatomic layer.Preferably 2 monoatomic layers to 5 monoatomic layers, the preferred number of plies being capable of guaranteed discharge Son point realizes good photoluminescence quantum yield and efficient charge injection efficiency.
Further, each monoatomic layer in A1 types and A2 type quantum-dot structure units is minimal structure list Member, i.e., its alloy compositions of each layer of single atomic layer are fixed, and may shape between two adjacent monoatomic layers Into graded alloy component structure, for example, in the quantum-dot structure unit of A1 types, it is monatomic far from luminescent material center Layer, Cd and Se contents are low, Zn and S contents are high, and the monoatomic layer close to luminescent material center, Cd and Se contents are low, Zn and S Content is high, so as to form graded alloy component structure.But in the quantum-dot structure unit of A2 types, each layer of monoatomic layer Its alloy compositions is identical, to form uniform alloy compositions structure.
Alternatively, the A1 types and A2 type quantum-dot structures unit include 1-10 layers of structure cell layer, i.e., each quantum Point structural unit includes 1-10 layers of structure cell layer, such as include 2-5 layers of structure cell layer.Structure cell layer is minimum structural unit, i.e., Its alloy compositions of each layer of structure cell layer are fixed, i.e., have identical lattice parameter and element in each structure cell layer.It is each Quantum-dot structure unit be structure cell layer it is continuously coupled and form closed unit cell curved surface.
Further, two of the quantum-dot structure unit intersection of adjacent graded alloy component structure in radial directions Continuous alloy compositions structure is formed between monoatomic layer.That is, the quantum-dot structure unit of two graded alloy component structures has a common boundary Be continuous alloy compositions structure between two monoatomic layers at place namely its level width be also gradual change rather than mutation. Alternatively, in radial directions between two structure cell layers of the quantum-dot structure unit intersection of adjacent graded alloy component structure Form continuous alloy compositions structure.The quantum-dot structure unit of adjacent graded alloy component structure mentioned above is adjacent The quantum-dot structure unit of A1 types.
That is, the present invention luminescent material, between adjacent A1 type quantum-dot structure units have from it is interior to Continuous alloy compositions radially outside.This quantum-dot structure has from inside to outside radially in constituent The characteristics of consecutive variations, relative to the relationship for clearly defining quantum dot core and shell, luminescent material of the invention is not only advantageous In the more efficient luminous efficiency of realization, while it also can more meet the synthesis of semiconductor devices and corresponding display technology to luminescent material Performance requirement is a kind of suitable semiconductor devices and the preferable quantum dot luminescent material of display technology.
The luminescent material of the present invention using the above structure, the photoluminescence quantum yield that can be realized ranging from 1% to 100% are excellent The photoluminescence quantum yield of choosing ranging from 30% to 100% can ensure the good of quantum dot in the range of preferred photoluminescence quantum yield Application.
The luminescent material of the present invention using the above structure, the glow peak wave-length coverage that can be realized are 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 Quanta point material realizes the photoluminescence quantum yield more than 30% within this range.
In the present invention, the peak width at half height of the glow peak of the luminescent material is 12 nanometers to 80 nanometers.
Luminescent material provided by the present invention has the advantages that：First, help to reduce difference to the full extent Lattice tension between the quantum dot crystal of alloy compositions simultaneously alleviates lattice mismatch, so as to reduce the formation of boundary defect, improves The luminous efficiency of quantum dot.Second, the level structure that luminescent material provided by the present invention is formed is more advantageous to quantum Effective constraint of electron cloud in point greatly reduces diffusion probability of the electron cloud to quantum dot surface, thus the greatly amount of inhibiting The auger recombination loss of son point radiationless transition, reduces quantum dot and flickers and improve quantum dot light emitting efficiency.Third, institute of the present invention The level structure that the luminescent material of offer is formed is more advantageous to improving the injection of quantum dot light emitting layer charge in semiconductor devices Efficiency and efficiency of transmission；It can effectively avoid the aggregation of charge and resulting Exciton quenching simultaneously.4th, institute of the present invention The easily controllable diversity level structure that the quanta point material of offer is formed can fully meet and other in coordination device The level structure of functional layer, to realize the matching of device entirety level structure, so as to help to realize efficient semiconductor devices.
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 luminescent material occurs between the first compound and second of chemical combination object, it is described to shine First there is blue shift in the glow peak wavelength of material, then constant.
Quantum dot SILAR synthetic methods incorporating quantum point one-step synthesis is generated luminescent material by the preparation method of the present invention, It is specially successively grown using quantum dot and forms graded component transitional crust using quantum dot one-step synthesis.It is being pre-positioned Putting place and successively being formed two layers has identical or different-alloy component compound thin film, is occurred between two layers of compound by making Cation exchange reaction is distributed so as to fulfill in the alloy compositions of pre-position.Repeating above procedure can constantly realize The alloy compositions distribution of radial direction pre-position.
Described the first compound and second of compound can be binary or binary more than compound.
Further, first there is continuous blue shift in the glow peak wavelength of the luminescent material, then constant.There is blue shift and represent hair Photopeak is moved to shortwave direction, and level width broadens, and it is constant to represent level width if the constant representative of glow peak wavelength.Such as Fig. 1 Shown, in quantum dot in the radial direction, level width broadens in first interval（Blue shift）, level width is not in second interval Become（It 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 anion presoma of the first described compound and/or second of compound includes the presoma of Se, example Can be specifically Se-TOP (selenium- if Se with some organic matters arbitrarily combines formed compound 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 includes the presoma of Te, institute The presoma for stating Te is Te-TOP, Te-TBP, Te-TPP, Te-ODE, Te-OA, Te-ODA, Te-TOA, Te-ODPA or Te-OLA At least one of.
Above-mentioned cation precursor and anion presoma can form to determine to select it according to final luminescent material One or more of：Such as it needs to synthesize CdxZn1-xSeyS1-yLuminescent material when, then need the presoma of Cd, the forerunner of Zn Body, the presoma of Se, S presoma；If desired for synthesis CdxZn1-xDuring the luminescent material of S, then the presoma of Cd, Zn are needed The presoma of presoma, S；If desired for synthesis CdxZn1-xDuring the luminescent material of Se, then need the presoma of Cd, the presoma of Zn, The presoma of Se.
In the preparation process in accordance with the present invention, the condition that cation exchange reaction occurs preferably carries out heating reaction, such as Heating temperature is between 100 DEG C to 400 DEG C, between preferred heating temperature is 150 DEG C to 380 DEG C.Heating time is in 2s to for 24 hours Between, preferred heating time is 5min between 4h.
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 luminescent material 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 luminescent material prepared by above-mentioned preparation method, glow peak wave-length coverage is 400 nanometers to 700 nanometers, Preferred glow peak wave-length coverage is 430 nanometers to 660 nanometers, and preferred quantum dot light emitting peak wave-length coverage can ensure quantum Point realizes the photoluminescence quantum yield more than 30% within this range.
Luminescent material prepared by method made above, photoluminescence quantum yield ranging from 1% to 100%, preferred luminous quantity Sub- yield ranging from 30% to 100% can ensure the applications well of quantum dot in the range of preferred photoluminescence quantum yield.
In the present invention, the peak width at half height of the glow peak of the luminescent 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 luminescent 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 carry out reacting the luminous material of formation with anion presoma Material, and first to occur blue shift during the reaction then constant for the glow peak wavelength of the luminescent material, so as to fulfill specified Graded alloy component distribution at position.
The difference of such method and former approach is, former is successively to form two layers of compound, Ran Houfa Raw cation exchange reaction, is distributed so as to fulfill graded alloy component, and later approach is directly controlled in pre-position The synthesis cationic presoma of alloy compositions and anion presoma needed for adding in carry out reaction and form luminescent material, so as to real Existing graded alloy component distribution of the present invention.For later approach, reaction principle be the high cationic presoma of reactivity and Anion presoma first reacts, and reacts after the low cationic presoma of reactivity and anion presoma, and During the reaction, cation exchange reaction occurs for different cations, is distributed so as to fulfill graded alloy component of the present invention.Extremely It has been described in detail in preceding method in the type of cationic presoma and anion presoma.As for reaction temperature, reaction time With proportioning etc. can the quanta point material of synthesis according to needed for specific it is different and different, with aforementioned former approach substantially It is identical, subsequently illustrated with specific embodiment.
The present invention also provides a kind of semiconductor devices, including as above any one of them luminescent material.
The semiconductor devices is electroluminescent device, photo luminescent devices, solar cell, display device, photoelectricity are visited Survey any one in device, bioprobe and device for non-linear optical.
By taking electroluminescent device as an example, the quanta point electroluminescent device using luminescent material of the present invention as luminescent layer Part.This quanta point electroluminescent device can be realized：1) high efficiency charge injection, 2) high brightness, 3) low driving electricity Pressure, 4) the excellent devices performance such as high device efficiency.Meanwhile quanta point material of the present invention, have easily controllable and various The characteristics of performance level structure, can fully meet the level structure of other functional layers in simultaneously coordination device, to realize device entirety The matching of level structure, so as to help to realize the semiconductor devices of efficient stable.
The photo luminescent devices refer to that relying on external light source is irradiated, and so as to obtain energy, generating excitation causes to send out The device of light, ultraviolet radioactive, visible ray and infra-red radiation can cause luminescence generated by light, such as phosphorescence and fluorescence.The hair of the present invention Luminescent material can be as the luminescent material of photo luminescent devices.
The solar cell is also referred to as photovoltaic device, and luminescent material of the invention can be as the light absorption material of solar cell Material effectively improves the properties of photovoltaic device.
The display device refers to the display panel of backlight module or the application backlight module, and the display panel can be with It applies in various products, such as display, tablet computer, mobile phone, laptop, flat panel TV, wearable display Equipment or other include the products of different size display panels.
The photodetector refers to optical signal can be converted to the device of electric signal, and principle is to be caused to be shone by radiation It penetrates material electric conductivity to change, quanta point material is applied in photodetector, there is following advantage：To vertical incidence light Sensitive, photoconductive response degree height, specific detecivity are high, detection wavelength is continuously adjusted and can low temperature preparation.The photoelectricity of this structure is visited Survey device in the process of running, quantum dot light photosensitive layer（Luminescent material i.e. using the present invention）Absorb the photoproduction electricity generated after photon To can be detached under the action of built in field, this causes the structure photodetector to have lower driving in son-hole Voltage can just work, and easily controllable under low applying bias even 0 applying bias.
The bioprobe refers to modify certain class material, makes it have the device of mark function, such as to this hair Bright luminescent material is coated, and so as to form fluorescence probe, is applied in cell imaging or substance detection field, relative to Traditional organic fluorescent dye probe, bioprobe prepared by nanocrystal using the present invention have fluorescence intensity height, chemistry The characteristics of stability is good, anti-light bleaching power is strong, tool has been widely used.
The device for non-linear optical belongs to optical lasers technical field, using wide, such as opens the light for electric light And Laser Modulation, the tuning of conversion, laser frequency for laser frequency；Carry out optical Information Processing, improve image quality and Beam quality；As nonlinear etalon and bistable device；The highly excited level and high-resolution spectroscopy and object of research substance Transfer process and other relaxation processes of matter internal energy and excitation etc..
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 Quantum Well
It is prepared by sour cadmium and oleic acid zinc precursor：By 1 mmol cadmium oxides（CdO）, 9 mmol zinc acetates [Zn (acet) 2], 8 mL oil 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 true 60 min of sky degassing.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 Quantum Well（CdxZn1-xS）.
Embodiment 11：The preparation of green quantum dot with Quantum Well
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 Quantum Well（CdxZn1-xSeyS1-y/ZnS）.
Embodiment 12：The preparation of red quantum dot with Quantum Well
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, CdxZn1-xSe is nucleated rapidly, and after reacting 10 min, temperature of reaction system is down to 280 DEG C, will Selenizing tri octyl phosphine-trioctylphosphine sulfide 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 having amount The red quantum dot of sub- trap level structure（CdxZn1-xSe/ZnSeS）.
Embodiment 13
The present embodiment light emitting diode with quantum dots, as shown in Fig. 2, including successively from bottom to top：ITO substrates 11, hearth electrode 12, PEDOT：PSS hole injection layers 13, poly-TPD hole transmission layers 14, quantum dot light emitting layer 15, ZnO electron transfer layers 16 and Al Top electrode 17.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows：
Hearth electrode 12,30 nm PEDOT are sequentially prepared on ITO substrates 11：13 and 30 nm poly-TPD of PSS hole injection layers After hole transmission layer 14, one layer of quantum dot light emitting layer 15 is prepared on poly-TPD hole transmission layers 14, thickness is 20 nm, with Prepare 40 nm ZnO electron transfer layers 16 and 100 nm Al top electrodes 17 on quantum dot light emitting layer 15 again afterwards.The quantum dot The luminescent material of luminescent layer 15 is luminescent material as described in Example 10.
Embodiment 14
Light emitting diode with quantum dots in the present embodiment, as shown in figure 3, including successively from bottom to top：ITO substrates 21, hearth electrode 22, PEDOT：PSS hole injection layers 23, Poly (9-vinylcarbazole) (PVK) hole transmission layer 24, quantum dot light emitting layer 25th, ZnO electron transfer layers 26 and Al top electrodes 27.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows：
Hearth electrode 22,30 nm PEDOT are sequentially prepared on ITO substrates 21：23 and 30 nm PVK holes of PSS hole injection layers After transport layer 24, one layer of quantum dot light emitting layer 25 is prepared on PVK hole transmission layers 24, thickness is 20 nm, then again in quantum 40 nm ZnO electron transfer layers 26 and 100 nm Al top electrodes 27 are prepared on point luminescent layer 25.The quantum dot light emitting layer 25 Luminescent material is luminescent material as described in Example 11.
Embodiment 15
The present embodiment light emitting diode with quantum dots, as shown in figure 4, including successively from bottom to top：ITO substrates 31, hearth electrode 32, PEDOT：PSS hole injection layers 33, poly-TPD hole transmission layers 34, quantum dot light emitting layer 35, TPBi electron transfer layers 36 and Al top electrodes 37.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows：
Hearth electrode 32,30 nm PEDOT are sequentially prepared on ITO substrates 31：33 and 30 nm poly-TPD of PSS hole injection layers After hole transmission layer 34, one layer of quantum dot light emitting layer 35 is prepared on poly-TPD hole transmission layers 34, thickness is 20 nm, with 30 nm TPBi electron transfer layers 36 are prepared by vacuum deposition method on quantum dot light emitting layer 35 again afterwards and 100 nm Al are pushed up Electrode 37.The luminescent material of the quantum dot light emitting layer 35 is luminescent material as described in Example 12.
Embodiment 16
The present embodiment light emitting diode with quantum dots, as shown in figure 5, including successively from bottom to top：ITO substrates 41, hearth electrode 42, ZnO electron transfer layers 43, quantum dot light emitting layer 44, NPB hole transmission layers 45, MoO3Hole injection layer 46 and Al top electrodes 47.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows：
42,40 nm ZnO electron transfer layers 43 of hearth electrode are sequentially prepared on ITO substrates 41, on ZnO electron transfer layers 43 One layer of quantum dot light emitting layer 44 is prepared, thickness is 20 nm, then prepares 30 nm NPB holes by vacuum deposition method again 45,5 nm MoO of transport layer346 and 100 nm Al top electrodes 47 of hole injection layer.The luminous material of the quantum dot light emitting layer 44 Expect for luminescent material as described in Example 10.
Embodiment 17
The present embodiment light emitting diode with quantum dots, as shown in fig. 6, including successively from bottom to top：Glass substrate 51, Al electrodes 52, PEDOT：PSS hole injection layers 53, poly-TPD hole transmission layers 54, quantum dot light emitting layer 55, ZnO electron transfer layers 56 and ITO top electrodes 57.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows：
100 nm Al electrodes 52 are prepared by vacuum deposition method in glass substrate 51, are then sequentially prepared 30 nm PEDOT：After 53 and 30 nm poly-TPD hole transmission layers 54 of PSS hole injection layers, on poly-TPD hole transmission layers 54 One layer of quantum dot light emitting layer 55 is prepared, thickness is 20 nm, then prepares 40 nm ZnO electronics on quantum dot light emitting layer 55 again Transport layer 56 prepares 120 nm ITO as top electrode 57 finally by sputtering method.The quantum dot light emitting layer 55 shines Material is luminescent material as described in Example 11.
Embodiment 18
The present embodiment light emitting diode with quantum dots, as shown in fig. 7, including successively from bottom to top：Glass substrate 61, Al electrodes 62, ZnO electron transfer layers 63, quantum dot light emitting layer 64, NPB hole transmission layers 65, MoO3Hole injection layer 66 and ITO top electrodes 67.
The preparation process of above-mentioned light emitting diode with quantum dots is as follows：
100 nm Al electrodes 62 are prepared by vacuum deposition method in glass substrate 61, are then sequentially prepared 40 nm ZnO 63,20 nm quantum dot light emitting layers 64 of electron transfer layer then prepare 30 nm NPB hole transports by vacuum deposition method again 65,5 nm MoO of layer3Hole injection layer 66 prepares 120 nm ITO as top electrode 67 finally by sputtering method.The amount The luminescent material of son point luminescent layer is luminescent material as described in Example 12.
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 (22)

1. a kind of luminescent material with funnel type level structure, which is characterized in that the luminescent material includes N number of in radial direction side The quantum-dot structure unit arranged successively upwards, wherein N >=2；
The quantum-dot structure unit includes A1 and A2 types, and the A1 types are wider for more outside level width in the radial direction Graded alloy component structure；The A2 types are the consistent homogeneous components structure of level width in the radial direction；
The inside of the luminescent material is made of the quantum-dot structure unit of at least one layer of A1 types, the outside of the luminescent material It is made of the quantum-dot structure unit of at least one layer of A2 types；
In radial directions in adjacent quantum-dot structure unit, close to the energy level of the quantum-dot structure unit at luminescent material center Width is not more than the level width of the quantum-dot structure unit far from luminescent material center；And adjacent graded alloy component structure The energy level of quantum-dot structure unit be continuous.
2. luminescent material according to claim 1, which is characterized in that the quantum-dot structure unit of the A1 types be comprising II races and the graded alloy component structure of VI races element, the quantum-dot structure unit of the A2 types is comprising II races and VI races member The uniform alloy compositions structure of element.
3. luminescent material according to claim 2, which is characterized in that the alloy of the quantum-dot structure unit of the A1 types Component is Cdx0Zn1-x0Sey0S1-y0, wherein 0≤x0≤1,0≤y0≤1, and it is 0 during x0 with y0 differences and is asynchronously 1.
4. luminescent material according to claim 2, which is characterized in that the alloy of the quantum-dot structure unit of the A2 types Group is grouped into Cdx1Zn1-x1Sey1S1-y1, wherein 0≤x1≤1,0≤y1≤1, and it is 0 during x1 with y1 differences and is asynchronously 1, and x1 and y1 is fixed value in the quantum-dot structure unit of corresponding A2 types.
5. luminescent material according to claim 3, which is characterized in that in the quantum-dot structure unit of the A1 types, A points Alloy compositions be 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 are closer to luminescent material center, and the composition of A points and B points meets：x0 A>x0 B,y0 A >y0 B。
6. luminescent material according to claim 1, which is characterized in that the quantum-dot structure unit includes 2-20 layers of list Atomic layer or the quantum-dot structure unit include 1-10 layers of structure cell layer.
7. luminescent material according to claim 6, which is characterized in that adjacent quantum-dot structure unit in radial directions Continuous alloy compositions structure or quantum-dot structure adjacent in radial directions are formed between two monoatomic layers of intersection Continuous alloy compositions structure is formed between two structure cell layers of unit intersection.
8. luminescent material according to claim 1, which is characterized in that the glow peak wave-length coverage of the luminescent material is 400 nanometers to 700 nanometers.
9. luminescent material according to claim 1, which is characterized in that the peak width at half height of the glow peak of the luminescent material is 12 nanometers to 80 nanometers.
10. a kind of preparation method of luminescent material as described in claim 1, which is characterized in that 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 luminescent material occurs between the first compound and second of chemical combination object, it is described to shine First there is blue shift in the glow peak wavelength of material, then constant.
11. the preparation method of luminescent material according to claim 10, which is characterized in that the first described compound and/ Or the cationic presoma of second of compound includes the presoma of Zn, the presoma of the Zn is zinc methide, diethyl Base zinc, zinc acetate, zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, zinc nitrate, oxidation At least one of zinc, zinc peroxide, zinc perchlorate, zinc sulfate, zinc oleate or zinc stearate.
12. the preparation method of luminescent material according to claim 10, which is characterized in that the first described compound and/ Or the cationic presoma of second of compound further includes the presoma of Cd, the presoma of the Cd is dimethyl cadmium, two Ethyl-cadmium, cadmium acetate, acetylacetone,2,4-pentanedione cadmium, cadmium iodide, cadmium bromide, caddy, cadmium fluoride, cadmium carbonate, cadmium nitrate, cadmium oxide, height At least one of cadmium chlorate, cadmium phosphate, cadmium sulfate, cadmium oleate or cadmium stearate.
13. the preparation method of luminescent material according to claim 10, which is characterized in that the first described compound and/ Or the anion presoma of second of compound includes the presoma of Se, the presoma of the Se is Se-TOP, Se-TBP, At least one of Se-TPP, Se-ODE, Se-OA, Se-ODA, Se-TOA, Se-ODPA or Se-OLA.
14. the preparation method of luminescent material according to claim 10, which is characterized in that the first described compound and/ Or the anion presoma of second of compound further includes the presoma of S, the presoma of the S is S-TOP, S-TBP, S- At least one of TPP, S-ODE, S-OA, S-ODA, S-TOA, S-ODPA, S-OLA or alkyl hydrosulfide.
15. the preparation method of luminescent material according to claim 10, which is characterized in that the first described compound and/ Or the anion presoma of second of compound further includes the presoma of Te, the presoma of the Te is Te-TOP, Te-TBP, At least one of Te-TPP, Te-ODE, Te-OA, Te-ODA, Te-TOA, Te-ODPA or Te-OLA.
16. the preparation method of luminescent material according to claim 10, which is characterized in that make the first in a heated condition Cation exchange reaction occurs between compound and second of chemical combination object.
17. the preparation method of luminescent material according to claim 16, which is characterized in that heating temperature is at 100 DEG C to 400 Between DEG C.
18. the preparation method of luminescent material according to claim 16, which is characterized in that heating time 2s to for 24 hours it Between.
19. the preparation method of luminescent material according to claim 10, which is characterized in that synthesizing the first compound When, the molar ratio of cationic presoma and anion presoma is 100:1 to 1:Between 50.
20. the preparation method of luminescent material according to claim 10, which is characterized in that synthesizing second of compound When, the molar ratio of cationic presoma and anion presoma is 100:1 to 1:Between 50.
21. a kind of semiconductor devices, which is characterized in that including such as claim 1 ~ 9 any one of them luminescent material.
22. semiconductor devices according to claim 21, which is characterized in that the semiconductor devices is electroluminescent cell In part, photo luminescent devices, solar cell, display device, photodetector, bioprobe and device for non-linear optical Any one.
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