CN109449312A - The heat auxiliary vacuum evaporation preparation method of inorganic perovskite light emitting diode - Google Patents

The heat auxiliary vacuum evaporation preparation method of inorganic perovskite light emitting diode Download PDF

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Publication number
CN109449312A
CN109449312A CN201811086428.7A CN201811086428A CN109449312A CN 109449312 A CN109449312 A CN 109449312A CN 201811086428 A CN201811086428 A CN 201811086428A CN 109449312 A CN109449312 A CN 109449312A
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layer
cspbbr
light emitting
emitting diode
poly
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宋继中
韩博宁
陈嘉伟
方涛
曾海波
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0694—Halides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention discloses a kind of heat auxiliary vacuum evaporation preparation methods of inorganic perovskite light emitting diode.First poly- (styrene sulfonate) hole injection layer of spin coating Polyglycolic acid fibre-on ito glass of the method, is then spin coated onto hole transmission layer, then passes through Vacuum sublimation for CsPbBr3It deposits to and heats the substrate, finally by thermal evaporation deposition electron transfer layer and metal electrode, obtain the uniform CsPbBr that shines3Inorganic perovskite light emitting diode.The present invention passes through to CsPbBr3Perovskite deposition substrate carries out hot auxiliary temperature regulation, obtains the perovskite luminescent layer of even compact, CsPbBr obtained3Inorganic perovskite lumination of light emitting diode uniformly and high brightness.

Description

The heat auxiliary vacuum evaporation preparation method of inorganic perovskite light emitting diode
Technical field
The present invention relates to a kind of CsPbBr3The heat auxiliary vacuum evaporation preparation method of inorganic perovskite light emitting diode, belongs to In electroluminescent device preparation technical field.
Background technique
Halide perovskite material has outstanding photoelectric properties and higher energy transformation ratio, in light emitting diode, too Positive energy battery and laser etc. fields are widely used.With organic inorganic hybridization perovskite (CH3NH3PbX3) compare, inorganic perovskite (CsPbX3) excellent stability is shown, there is huge potential using value in photoelectronics.
In the developmental research of perovskite photoelectric device, numerous preparation processes is exploited, wherein vacuum evaporation skill Art presents leading advantage, for example, large area controllable preparation, solvent-free green preparation process and thickness precision are controllable Deng.These advantageous characteristics make vacuum evaporation technology become face the future on a large scale can the best of industrialized production can development process. Although vacuum evaporation prepares perovskite, film layer technology has considerable development prospect, is still solution using most at present Technique is primarily due to the perovskite film pattern of vacuum evaporation not easy-regulating, and obtained film layer is not fine and close enough, causes it corresponding Device performance is poor, so the smooth fine and close perovskite thin film of preparation is most important.Document (Ling Y, et al.The Journal of Physcial Chemistry Letters, 2017,8,3266-3271) by the resulting perovskite of deposition Film carries out heating post-processing, promotes film performance, but deposition and heat treatment are carried out in two steps, technique is cumbersome.
Summary of the invention
The purpose of the present invention is to provide a kind of heat auxiliary vacuum evaporation preparation methods of inorganic perovskite light emitting diode. This method is using heat auxiliary vacuum vapour deposition, by CsPbBr3Perovskite deposition substrate carry out heat treatment prepare it is high-incidence The CsPbBr of brightness3Inorganic perovskite light emitting diode.
Realize that the technical solution of the object of the invention is as follows:
The heat auxiliary vacuum evaporation preparation method of inorganic perovskite light emitting diode, the first poly- ethylene of spin coating on ito glass Poly- (styrene sulfonate) hole injection layer of dioxy thiophene-is then spin coated onto hole transmission layer, then will by vacuum thermal evaporation CsPbBr3It deposits to and heats the substrate, finally by thermal evaporation deposition electron transfer layer and metal electrode, obtain shining uniform CsPbBr3Inorganic perovskite light emitting diode, the specific steps are as follows:
Step 1, spin coating hole injection layer Polyglycolic acid fibre-poly- (styrene sulfonate) on clean ito glass Solution is heat-treated at 90 DEG C~140 DEG C, obtains hole injection layer；
Step 2, in the surface spin coating hole transmission layer solution of hole injection layer, hot place is carried out at 100 DEG C~150 DEG C Reason, obtains hole transmission layer；
Step 3, using Vacuum sublimation by CsPbBr3Perovskite luminescent layer deposits to hole transport layer surface, simultaneously Hot aid in treatment is carried out at 100 DEG C~120 DEG C, obtains luminescent layer；
Step 4, electron transfer layer 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) is deposited on the surface of luminescent layer Benzene；
Step 5, in the surface thermal evaporation deposition electrode material LiF/Al of electron transfer layer, CsPbBr is obtained3Inorganic calcium titanium Mine light emitting diode.
Preferably, in step 1, the concentration of poly- (styrene sulfonate) solution of the Polyglycolic acid fibre-is 1.3~ 1.7wt%；Spin coating is with a thickness of 30~60nm.
Preferably, in step 2, the hole transmission layer solution be selected from poly- [bis- (4- phenyl) (4- butyl phenyl) amine], Poly- [(9,9- di-n-octyl fluorenyl -2,7- diyl)-alt- (4,4 '-(4- normal-butyl) phenyl)-diphenylamines] or poly- [bis- (4- benzene Base) (2,4,6- trimethylphenyl) amine]；Spin coating is with a thickness of 5~20nm.
Preferably, in step 3, the CsPbBr3The deposition thickness of perovskite luminescent layer is 20~30nm.
Preferably, in step 4, the deposition thickness of the electron transfer layer is 30~50nm.
Preferably, in step 5, the deposition thickness of the electrode material LiF/Al is 1nm/80~100nm.
Compared with prior art, the invention has the following advantages that
(1) present invention deposits the CsPbBr of smooth densification using heat auxiliary vacuum vapour deposition3Luminescent layer, preparation process letter Single, mild condition is at low cost；
(2) CsPbBr prepared by the present invention3The brightness of inorganic perovskite light emitting diode is high, and excitation purity is high.
Detailed description of the invention
Fig. 1 is that the heat auxiliary vacuum vapour deposition that embodiment 1 uses deposits CsPbBr3Schematic diagram.
The CsPbBr that Fig. 2 is embodiment 1 (a), prepared by comparative example 1 (b), comparative example 2 (c), comparative example 3 (d)3Film AFM figure.
Fig. 3 is luminous diode device structure schematic diagram prepared by embodiment 1.
Fig. 4 is lumination of light emitting diode spectrogram prepared by embodiment 1.
The electricity for the light emitting diode that Fig. 5 is embodiment 1 (a), prepared by comparative example 1 (b), comparative example 2 (c), comparative example 3 (d) The relational graph of current density and brightness and driving voltage.
Specific embodiment
Below by way of specific embodiment and attached drawing, the invention will be further described.
Embodiment 1
1) poly- (styrene sulfonate) solution of spin coating Polyglycolic acid fibre-, revolving speed are on cleaned ito glass 3000r/min heats 15min at 150 DEG C；
2) poly- [bis- (4- phenyl) (4- butyl phenyl) amine] solution of spin coating, revolving speed 3000r/min；
3) while carrying out 100 DEG C~120 DEG C heat treatment to substrate, method is steamed using Vacuum Heat and deposits CsPbBr3Calcium titanium Mine luminescent layer, concrete technology schematic diagram are shown in Fig. 1, deposit resulting CsPbBr3Film is shown in Fig. 2；
4) TPBi, deposition thickness 40nm are deposited by thermal evaporation；
5) LiF/Al electrode is deposited using mask plate by thermal evaporation, LiF/Al thickness of electrode is 1nm/100nm, is made CsPbBr3Inorganic perovskite light emitting diode, structural schematic diagram are shown in Fig. 3, obtained halfwidth be only 17nm high-purity it is green Light, lumination of light emitting diode map are shown in Fig. 4, while the note of carrier in device is improved by the regulation to substrate heating temperature Enter with it is compound, so that current density and brightness is got a promotion, the relational graph of current density and brightness and driving voltage is shown in Fig. 5.
Embodiment 2
Similar to Example 1, difference is, by poly- [bis- (4- phenyl) (the 4- butyl phenyl) in the step 2) of embodiment 1 Amine] it is changed to poly- [(9,9- di-n-octyl fluorenyl -2,7- diyl)-alt- (4,4 '-(4- normal-butyl) phenyl)-diphenylamines], other Condition is consistent, and CsPbBr is made3Inorganic perovskite light emitting diode.
Embodiment 3
Similar to Example 1, difference is, by poly- [bis- (4- phenyl) (the 4- butyl phenyl) in the step 2) of embodiment 1 Amine] it is changed to poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine], other conditions are consistent, and CsPbBr is made3Inorganic calcium Titanium ore light emitting diode.
Comparative example 1
Similar to Example 1, difference is, by the substrate of the step 3) of embodiment 1 without heat treatment, other conditions It is consistent, CsPbBr is made3Inorganic perovskite light emitting diode.
Comparative example 2
Similar to Example 1, difference is, the substrate of the step 3) of embodiment 1 is carried out 60 DEG C of heat treatment, other Part is consistent, and CsPbBr is made3Inorganic perovskite light emitting diode.
Comparative example 3
Similar to Example 1, difference is, the substrate of the step 3) of embodiment 1 is carried out 180 DEG C of heat treatment, other Condition is consistent, and CsPbBr is made3Inorganic perovskite light emitting diode.

Claims (6)

1. the heat auxiliary vacuum evaporation preparation method of inorganic perovskite light emitting diode, which is characterized in that specific step is as follows:
Step 1, spin coating hole injection layer Polyglycolic acid fibre-poly- (styrene sulfonate) solution on clean ito glass, It is heat-treated at 90 DEG C~140 DEG C, obtains hole injection layer；
Step 2, it in the surface spin coating hole transmission layer solution of hole injection layer, is heat-treated, is obtained at 100 DEG C~150 DEG C To hole transmission layer；
Step 3, using Vacuum sublimation by CsPbBr3Perovskite luminescent layer deposits to hole transport layer surface, while 100 DEG C~120 DEG C at carry out hot aid in treatment, obtain luminescent layer；
Step 4, electron transfer layer 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene is deposited on the surface of luminescent layer；
Step 5, in the surface thermal evaporation deposition electrode material LiF/Al of electron transfer layer, CsPbBr is obtained3Inorganic perovskite shines Diode.
2. preparation method according to claim 1, which is characterized in that in step 1, the Polyglycolic acid fibre-is poly- The concentration of (styrene sulfonate) solution is 1.3~1.7wt%；Spin coating is with a thickness of 30~60nm.
3. preparation method according to claim 1, which is characterized in that in step 2, the hole transmission layer solution is selected from Poly- [bis- (4- phenyl) (4- butyl phenyl) amine], poly- [(9,9- di-n-octyl fluorenyl -2,7- diyl)-alt- (4,4 '-(positive fourths of 4- Base) phenyl)-diphenylamines] or it is poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine]；Spin coating is with a thickness of 5~20nm.
4. preparation method according to claim 1, which is characterized in that in step 3, the CsPbBr3Perovskite luminescent layer Deposition thickness be 20~30nm.
5. preparation method according to claim 1, which is characterized in that in step 4, the deposition of thick of the electron transfer layer Degree is 30~50nm.
6. preparation method according to claim 1, which is characterized in that in step 5, the electrode material LiF/Al's is heavy Product is with a thickness of 1nm/80~100nm.
CN201811086428.7A 2018-09-18 2018-09-18 The heat auxiliary vacuum evaporation preparation method of inorganic perovskite light emitting diode Pending CN109449312A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104393109A (en) * 2014-10-28 2015-03-04 合肥工业大学 Chemical vapor deposition preparation method for perovskite solar cell
CN104485425A (en) * 2014-12-08 2015-04-01 清华大学 Perovskite type material preparation method and equipment and machining method of photovoltaic device made from perovskite type material
CN105355794A (en) * 2015-10-29 2016-02-24 深港产学研基地 Method for using chemical vapor deposition method to prepare perovskite film solar cell
CN106661729A (en) * 2014-08-21 2017-05-10 学校法人冲绳科学技术大学院大学学园 System and method based on low-pressure chemical vapor deposition for fabricating perovskite film
CN107123706A (en) * 2017-04-07 2017-09-01 湖南大学 A kind of CVD builds CsPbBr3The method of nanometer sheet electroluminescent device
CN107275523A (en) * 2017-06-13 2017-10-20 苏州大学 Preparation method of pure inorganic perovskite light-emitting diode device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106661729A (en) * 2014-08-21 2017-05-10 学校法人冲绳科学技术大学院大学学园 System and method based on low-pressure chemical vapor deposition for fabricating perovskite film
CN104393109A (en) * 2014-10-28 2015-03-04 合肥工业大学 Chemical vapor deposition preparation method for perovskite solar cell
CN104485425A (en) * 2014-12-08 2015-04-01 清华大学 Perovskite type material preparation method and equipment and machining method of photovoltaic device made from perovskite type material
CN105355794A (en) * 2015-10-29 2016-02-24 深港产学研基地 Method for using chemical vapor deposition method to prepare perovskite film solar cell
CN107123706A (en) * 2017-04-07 2017-09-01 湖南大学 A kind of CVD builds CsPbBr3The method of nanometer sheet electroluminescent device
CN107275523A (en) * 2017-06-13 2017-10-20 苏州大学 Preparation method of pure inorganic perovskite light-emitting diode device

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Application publication date: 20190308