CN107611230A - A kind of perovskite/silicon heterogenous electroluminescent device and preparation method - Google Patents

A kind of perovskite/silicon heterogenous electroluminescent device and preparation method Download PDF

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CN107611230A
CN107611230A CN201710733302.3A CN201710733302A CN107611230A CN 107611230 A CN107611230 A CN 107611230A CN 201710733302 A CN201710733302 A CN 201710733302A CN 107611230 A CN107611230 A CN 107611230A
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layer
perovskite
electroluminescent device
silicon heterogenous
silicon
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徐骏
刘婧婧
李东珂
季阳
吴仰晴
林泽文
陈坤基
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Nanjing University
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Nanjing University
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Abstract

Perovskite/silicon heterogenous electroluminescent device, the structure of the perovskite electroluminescent device is respectively anode layer, hole transmission layer electronic barrier layer, luminescent layer, electric transmission hole blocking layer and cathode layer from bottom to top;Hole transmission layer electronic barrier layer is Si sills, including p Si, p Si+SiO2, p Si+SiC, p Si+SiN and non-crystalline silicon, including these but not limited to this;Luminescent layer is full-inorganic perovskite CsPbX3, X is the combination (X=Cl, Br, I) of unitary halogens or polynary halogens.

Description

A kind of perovskite/silicon heterogenous electroluminescent device and preparation method
First, technical field
The present invention relates to electroluminescent device, especially a kind of full-inorganic perovskite electroluminescent based on silicon substrate material The design and preparation of device architecture, using ZnO and Si sills respectively as electronics and hole transmission layer;The present invention especially relates to And the stability and luminous efficiency of perovskite device are improved using exchange drive pattern.
2nd, background technology
In recent years, halogen perovskite material achieves huge progress in terms of solar cell and causes the extensive pass of people Note.In addition, perovskite also has some other performances, for example, high carrier mobility, low Urbach energy, it is small this The diffusion length of gram displacement, low trap density and length is held in the palm, these performances make perovskite material have in photoelectric device application Great potentiality.Particularly, perovskite quantum dot fluorescence yield is high, emission peak is narrower and the position of emission peak can pass through Component and size regulation and control, are advantageously implemented full color light emitting diode.Researcher is the performance for improving perovskite light emitting diode Also many effort are made that.But because device inside electronics and hole transmission layer are organic material mostly, these materials are to water It is very sensitive with oxygen, be influence device stability the main reason for one of.
In order to improve the stability of device, first from the preferable full-inorganic perovskite quantum dot CsPbX of stability3(X= Cl, Br, I).Secondly the design of device architecture, from suitable electronics and hole transmission layer.Utilize the preferably inorganic material of stability Material replaces the organic material of less stable.Silicon (Si) is used as a kind of currently the most important elemental semiconductorses, is modern micro- The foundation stone of electronic industry, there is ripe preparation technology.By constructing silicon based hetero-junction structure, by with superior luminescence performance Perovskite material and silicon materials, which combine, to be prepared efficient electroluminescent device and can promote large area silicon based opto-electronicses collection Into development.We have constructed a kind of full-inorganic perovskite quantum/silicon heterogenous light emitting diode of new structure.ZnO and p- Si is respectively as the electronics and hole transmission layer of device, and ITO and Al are respectively as negative electrode and anode.Obtain two kinds of feux rouges and green glow Electroluminescent device, due to red light quantum point CsPbI3Relatively low potential barrier is formed with silicon, so, cut-in voltage is less than green glow device Part.We compared for device luminescent properties under direct current and AC conditions, find under higher current density, and AC bias reduces boundary Charge accumulated at face, the decay of device luminescent properties can be reduced.
3rd, the content of the invention
In order to solve the performance of device, the object of the invention is to provide a kind of low turn-on voltage of new structure, low cost Full-inorganic perovskite electroluminescent device and preparation method, it is adapted to stability and luminous efficiency that exchange driving improves device.
To achieve these goals, the present invention takes following technical scheme:Perovskite/silicon heterogenous electroluminescent device; The structure of the perovskite electroluminescent device is respectively anode layer, hole transmission layer-electronic barrier layer from bottom to top, lighted Layer, electric transmission-hole blocking layer and cathode layer;Hole transmission layer-electronic barrier layer is Si sills, including p-Si, p-Si+ SiO2, p-Si+SiC, p-Si+SiN and non-crystalline silicon etc., including these but be not limited to these;Luminescent layer is full-inorganic perovskite CsPbX3, X is the combination (X=Cl, Br, I) of unitary halogens or polynary halogens, used to represent material molecule Formula is CsPbCl3, CsPbBr3, CsPbI3, CsPbBr3-xIx, CsPbBr3-xClx
It is typically constructed:Anode A l, hole transmission layer-electronic barrier layer p-Si or p-Si+SiO2, luminescent layer CsPbX3, electricity Sub- transport layer-hole blocking layer ZnO, negative electrode ITO.
The preparation method of full-inorganic perovskite EL device:
1) p-Si or p-Si+SiO cleaned up2As hole transport-electronic blocking and substrate;
2) using PECVD or magnetically controlled sputter method in p-Si or p-Si+SiO2It is upper to grow SiO respectively2, SiN, SiC silicon substrate Material (including these but be not limited to these silica-base materials).
3) back side thermal evaporation Al films of Si substrates are as anode;
4) alloying Al films, in tube furnace N2400 ± 30 DEG C of 30 ± 5min of insulation in protective atmosphere;
5) in Si substrate face spin coating perovskite quantum dots (thickness range 30nm-150nm);
6) perovskite quantum dot is put into baking oven 60 ± 10 DEG C, 3 ± 1min dryings;
7) magnetron sputtering ZnO thin film (thickness range 30nm-100nm);
8) ITO films prepared by DC magnetron sputtering (thickness range 150nm-400nm);
9) test device performance is driven with DC-AC respectively, it is as follows exchanges drive condition:(1) square wave driving frequency 10HZ-100MHZ includes this scope but not limited to this, and dutycycle 20%-80% includes this scope but not limited to this (2) sine wave Driving frequency 10HZ-100MHZ includes this scope but not limited to this.Exchange driving type include sine wave and square wave driving but not It is limited to this.
Beneficial effects of the present invention:
(1), the inorganic perovskite CsPbX that the present invention selects3The efficient hair of high brightness can be realized as luminescent layer Light, and the band gap of quantum dot can be regulated and controled by changing the component of quantum dot, realize multi-color electroluminescent device.Perovskite amount Pn-junction can be formed between son point and p-Si, device shows good rectification feature.Energy band in device between layers of material Match somebody with somebody, electron transfer layer-hole blocking layer and hole transmission layer-electronic barrier layer can promote being efficiently injected into and passing for carrier Defeated, limiting carrier/exciton is abundant compound in luminescent layer, reduces the cut-in voltage of device.Devices Electroluminescent peak half-peak Width, high luminescent saturation degree is shown, change stabilization with the change device luminescent properties of voltage.Obtained device has height Feux rouges or green glow power output.
(2), compared with DC driven, ac driver part shows higher luminous intensity under identical bias.And Under higher bias, ac driver part shows good stability.
4th, illustrate
The silicon heterogenous EL device structure schematic diagram of Fig. 1 full-inorganic perovskites provided by the invention;
The silicon heterogenous EL device structure energy level design drawing of Fig. 2 full-inorganic perovskites provided by the invention;
The electroluminescent graph of Fig. 3 silicon heterogenous devices of full-inorganic perovskite provided by the invention, 3 (a) green light emitting layer are CsPbBr3Quantum dot, 3 (b) red light luminescent layer are CsPbI3Quantum dot;
The Current density-voltage graph of a relation of Fig. 4 silicon heterogenous electroluminescent devices of full-inorganic perovskite provided by the invention;
The electricity of Fig. 5 direct currents provided by the invention and the lower silicon heterogenous electroluminescent device of full-inorganic perovskite of exchange driving Pressure-luminous intensity relationship figure.Fig. 5 frequency 10HZ, dutycycle 50%, frequency range 10HZ-1MHZ.
Fig. 6 is that present invention exchange driving improves device luminous intensity data, DC voltage 4V, exchanges drive condition:10HZ、 50% dutycycle, Vpp 4V.
5th, embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, below in conjunction with specific embodiment, full-inorganic The silicon heterogenous electroluminescent device mentality of designing of perovskite is as follows:
The present invention provides a kind of silicon heterogenous electroluminescent device of full-inorganic perovskite, and device architecture is as shown in figure 1, under To being above followed successively by anode A l, hole transmission layer-electronic barrier layer p-Si, luminescent layer CsPbX3, electron transfer layer-hole blocking layer ZnO, negative electrode ITO.Device lights under additional DC driven or exchange driving, and Fig. 2 is the silicon heterogenous electricity of full-inorganic perovskite Electroluminescence device structure energy level design drawing.Luminescent layer is full-inorganic perovskite CsPbX in the present invention3, Fig. 3 is provided by the invention complete The electroluminescent graph of the silicon heterogenous green glow of inorganic perovskite and red device, green device luminescent layer is CsPbBr3Quantum dot, it is red Optical device luminescent layer is CsPbI3Quantum dot (outsourcing).
1) cleaning silicon chip, p-type monocrystalline substrate (resistivity is cleaned:1.5-3 Ω cm) it is used as hole transport electronic blocking Layer and substrate, are cleaned with RCA standard cleaning flows;
2) evaporating Al electrode, substrate is positioned in thermal evaporation chamber, Si back side evaporating Al film is as anode;
3) alloying, the Si pieces of evaporating Al are put into N in tube furnace2400 DEG C of insulation 30min of atmosphere;
4) (example one) is in Si substrate face spin coating green glows CsPbBr3Quantum dot is as luminescent layer, spincoating conditions:Concentration 10mg/ml, rotating speed 2000r/min, time 60s, thickness 60nm or so, experiment are carried out in an atmosphere;
(example two) is in Si substrate face spin coating feux rouges CsPbI3Quantum dot is as luminescent layer, CsPbI3Quantum dot concentration 10mg/ml, rotating speed 2000r/min, time 60s, thickness 60nm or so, experiment are carried out in an atmosphere;
5) sample after spin coating quantum dot is put into 60 DEG C of insulation 3min in baking oven;
6) for magnetron sputtering ZnO thin film as electric transmission hole blocking layer, thickness is 50nm or so;
7) ITO films prepared by DC magnetron sputtering is 13 Ω/mouth or so as negative electrode, sheet resistance, and ITO is photosphere;
8) I-E characteristic of device is tested:Fig. 4 is the electric current of the silicon heterogenous electroluminescent device of full-inorganic perovskite Density-voltage relationship figure, it is that the curent change of device is little to device plus backward voltage, when adding forward bias, electric current is obvious Increase, shows good rectification characteristic.
9) test DC driven and exchange the luminescent spectrum parameter of the lower device of driving:Alternating-current measurement method is as follows:Square wave drives Dynamic frequency 10HZ, dutycycle 50%.The silicon heterogenous electroluminescent device of full-inorganic perovskite under Fig. 5 direct currents and exchange driving Voltage-luminous intensity graph of a relation, under higher biased, exchange driving device decay it is slower, stability is improved.
10) Fig. 6 is that present invention exchange driving significantly improves device luminous intensity data, DC voltage 4V, exchange driving bar Part:10HZ, 50% dutycycle, the condition that Vpp is 4V have the luminous intensity significantly improved than direct current 4V.
Particular embodiments described above, the purpose of the present invention, technical scheme and beneficial effect are carried out further in detail Describe in detail it is bright, should be understood that the foregoing is only the present invention specific embodiment, be not intended to limit the invention, it is all Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., it should be included in the guarantor of the present invention Within the scope of shield.

Claims (5)

1. perovskite/silicon heterogenous electroluminescent device, it is characterized in that the structure of the perovskite electroluminescent device from lower and Upper is respectively anode layer, hole transmission layer-electronic barrier layer, luminescent layer, electric transmission-hole blocking layer and cathode layer;Hole Transport layer-electronic barrier layer is Si sills, including p-Si, p-Si+SiO2, p-Si+SiC, p-Si+SiN and non-crystalline silicon, bag Include these but not limited to this;Luminescent layer is full-inorganic perovskite CsPbX3, X is the group of unitary halogens or polynary halogens Close (X=Cl, Br, I), the used molecular formula for representing material is CsPbCl3, CsPbBr3, CsPbI3, CsPbBr3-xIx, CsPbBr3-xClx
2. perovskite/silicon heterogenous electroluminescent device, it is characterized in that electroluminescent device is typically constructed:Anode A l, hole Transport layer-electronic barrier layer p-Si, luminescent layer CsPbX3, electron transfer layer-hole blocking layer ZnO, negative electrode ITO.
3. perovskite/silicon heterogenous electroluminescent device, it is characterized in that luminescent layer CsPbX3In Si substrate face spin coating perovskite amounts Son point obtains thickness range 30nm-150nm;Magnetron sputtering ZnO thin film thickness range 30nm-100nm;ITO films prepared by DC magnetron sputtering Thickness range 150nm-400nm.
4. the preparation method of perovskite/silicon heterogenous electroluminescent device, it is characterized in that:
1) p-Si or p-Si+SiO cleaned up2As hole transport-electronic blocking and substrate;
2) using PECVD or magnetically controlled sputter method in p-Si or p-Si+SiO2It is upper to grow SiO respectively2, SiN, SiC silica-base material (including these but be not limited to these silica-base materials).
3) back side thermal evaporation Al films of Si substrates are as anode;
4) alloying Al films, in tube furnace N2400 ± 30 DEG C of 30 ± 5min of insulation in protective atmosphere;
5) in Si substrate face spin coating perovskite quantum dots, concentration 5mg/ml-10mg/ml;
6) perovskite quantum dot is put into baking oven 60 ± 10 DEG C, 3 ± 1min dryings;
7) magnetron sputtering ZnO thin film thickness range 30nm-100nm;
8) ITO films prepared by DC magnetron sputtering thickness range 150nm-400nm.
5. the preparation method of perovskite according to claim 4/silicon heterogenous electroluminescent device, it is characterized in that CsPbBr3 Quantum dot is prepared into green light emitting layer, CsPbI3Quantum dot is prepared into red light luminescent layer.
CN201710733302.3A 2017-08-24 2017-08-24 A kind of perovskite/silicon heterogenous electroluminescent device and preparation method Pending CN107611230A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109524515A (en) * 2018-02-28 2019-03-26 湖北大学 One kind being based on GaN/CsPbBrxI3-xPhotoresponse type LED of hetero-junctions and its preparation method and application
CN110767816A (en) * 2019-11-29 2020-02-07 福州大学 Perovskite LED for alternating current driving and preparation method thereof
CN113380911A (en) * 2021-06-09 2021-09-10 哈尔滨工业大学 Preparation method of heterojunction material and photoelectric potential sensor based on halogen perovskite-boron doped silicon
CN113611782A (en) * 2021-07-27 2021-11-05 武汉大学 Perovskite micron plate-based efficient green light LED and preparation method thereof

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CN102157655A (en) * 2011-02-28 2011-08-17 浙江大学 Strontium titanate/P-type silicon heterojunction-based electroluminescent device and preparation method thereof
US20150287927A1 (en) * 2012-10-10 2015-10-08 Konica Minolta, Inc. Electroluminescence element
CN106549109A (en) * 2016-10-25 2017-03-29 Tcl集团股份有限公司 A kind of QLED devices based on p i n structures and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101707231A (en) * 2009-07-06 2010-05-12 中国科学院长春光学精密机械与物理研究所 New method for realizing efficient electrofluorescence and low threshold laser
CN102157655A (en) * 2011-02-28 2011-08-17 浙江大学 Strontium titanate/P-type silicon heterojunction-based electroluminescent device and preparation method thereof
US20150287927A1 (en) * 2012-10-10 2015-10-08 Konica Minolta, Inc. Electroluminescence element
CN106549109A (en) * 2016-10-25 2017-03-29 Tcl集团股份有限公司 A kind of QLED devices based on p i n structures and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109524515A (en) * 2018-02-28 2019-03-26 湖北大学 One kind being based on GaN/CsPbBrxI3-xPhotoresponse type LED of hetero-junctions and its preparation method and application
CN110767816A (en) * 2019-11-29 2020-02-07 福州大学 Perovskite LED for alternating current driving and preparation method thereof
CN113380911A (en) * 2021-06-09 2021-09-10 哈尔滨工业大学 Preparation method of heterojunction material and photoelectric potential sensor based on halogen perovskite-boron doped silicon
CN113611782A (en) * 2021-07-27 2021-11-05 武汉大学 Perovskite micron plate-based efficient green light LED and preparation method thereof

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