CN108198814B - Optical detection and electroluminescence dual-function integrated device and preparation method and application thereof - Google Patents
Optical detection and electroluminescence dual-function integrated device and preparation method and application thereof Download PDFInfo
- Publication number
- CN108198814B CN108198814B CN201810166532.0A CN201810166532A CN108198814B CN 108198814 B CN108198814 B CN 108198814B CN 201810166532 A CN201810166532 A CN 201810166532A CN 108198814 B CN108198814 B CN 108198814B
- Authority
- CN
- China
- Prior art keywords
- semiconductor layer
- type semiconductor
- integrated device
- dual
- bottom electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000001514 detection method Methods 0.000 title claims abstract description 22
- 238000005401 electroluminescence Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 14
- 230000003287 optical effect Effects 0.000 title description 10
- 239000004065 semiconductor Substances 0.000 claims abstract description 72
- 239000004005 microsphere Substances 0.000 claims abstract description 33
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000010410 layer Substances 0.000 claims description 119
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 238000000137 annealing Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 24
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 20
- 238000004891 communication Methods 0.000 claims description 15
- 230000001588 bifunctional effect Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 10
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 10
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 10
- 229960000999 sodium citrate dihydrate Drugs 0.000 claims description 10
- 239000011229 interlayer Substances 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- 230000002452 interceptive effect Effects 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000013307 optical fiber Substances 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 230000004298 light response Effects 0.000 abstract description 4
- 238000000825 ultraviolet detection Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 52
- 230000009977 dual effect Effects 0.000 description 22
- 238000005406 washing Methods 0.000 description 17
- 239000011521 glass Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000004044 response Effects 0.000 description 10
- 238000004528 spin coating Methods 0.000 description 9
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 8
- 229910052738 indium Inorganic materials 0.000 description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000012858 packaging process Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 241000208140 Acer Species 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 208000000453 Skin Neoplasms Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000023077 detection of light stimulus Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 201000000849 skin cancer Diseases 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/0203—Particular design considerations for integrated circuits
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/12—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Led Devices (AREA)
Abstract
The invention provides a light detection and electroluminescence dual-function integrated device which comprises a bottom electrode, an n-type semiconductor layer arranged on the upper surface of the bottom electrode, an i-type intermediate layer arranged on the upper surface of the n-type semiconductor layer, a p-type semiconductor layer arranged on the upper surface of the i-type intermediate layer and a top electrode arranged on the upper surface of the p-type semiconductor layer, wherein the n-type semiconductor layer is formed by ZnO microspheres, and the i-type intermediate layer is formed by CsPbBr3And forming the p-type semiconductor layer which is a GaN substrate doped with Mg. The dual-function integrated device provided by the invention realizes high-responsivity ultraviolet detection and ultra-pure green light emission. The invention utilizes the separation of the active layers for light emission and detection, obtains the dual-function integrated device with different electroluminescent areas and light response wave bands for the first time, effectively avoids the mutual reduction of the light emission and detection performances, and has huge application potential.
Description
Technical Field
The invention relates to the technical field of optical detection and electroluminescence, in particular to an optical detection and electroluminescence dual-function integrated device and a preparation method and application thereof.
Background
How to prepare a Light Emitting Diode (LED) with high efficiency, long life, safety and stable performance is becoming the focus of research. However, the LED may be an optical sensor, as well as a light emitting display function. As early as 1970, forrestm.mems (f.m.mems, silicon connections: com of organic electronics, McGraw-Hill Companies, 1986; f.m.mems III, l.circuitries, inc., new york, NY 1973,60.) has systematically introduced interactions between solid state luminescence and detection. Under forward bias, electrons and holes are injected into the junction region, and recombination radiation emits light; under 0V or negative bias, a built-in electric field separates photo-generated electron-hole pairs to realize the detection of light. In recent years, the capability of having the dual-functional properties of optical response and electroluminescence shows a great application prospect in the field of interactive communication systems. Recently, Oh et al (n.oh, b.h.kim, s. -y.cho, s.nam, s.p.rogers, y.jiang, j.c.flangan, y.zhai, j. -h.kim, j.lee, Science 2017,355,616.) pushed this dual function feature to a new height, and they designed "double heterojunction" colloidal semiconductor nanorods using quantum dot technology, to realize both electroluminescent and photocurrent-based photovoltaic responses in one LED device, allowing the LED device to emit both light and detect optical signals. In their reports, it is important to demonstrate how to implement the functions of contactless interactive display screens to energy harvesting and clear displays using these dual function diode arrays. In addition, the LED devices can also be applied to massive parallel data communication between displays.
Although such dual function devices have great application prospects, they are contradictory in terms of theoretical mechanism. Based on a carrier transport theory, photoelectric response requires: when photons irradiate the pn junction, the generated electron-hole pairs (when the photon energy is larger than the forbidden bandwidth of the semiconductor) are separated under an internal electric field (or an external bias), and finally photocurrent is generated; for the LED, under an external internal field, electron holes are bound in a semiconductor to finally realize compound light emission. Thus, for a material device, the luminescent performance of the material device is inevitably weakened due to the good photoelectric response performance, and therefore, a luminescent and detecting device with high performance simultaneously faces a great challenge. For example Yasuhiro Shiraki et al (x.xu, t.chiba, t.maruizumi, y.shiraki, Lasers and Electro-Optics Pacific Rim,2013.) use Ge quantum dots as functional materials, easily achieve a photoelectric response with a switching ratio as high as 104, but this device has problems of impure chromaticity in electroluminescence and the like. Heeger et al (G.Yu, C.Zhang, A.J.Heeger, applied Physics Letters 1994,64,1540.) similarly obtained nearly 10 using polymer (2-methoxy-5- (2' -ethyl-hexyloxy) -l,4-phenylene vinylene) as the functional material4But the external quantum effect of the device electroluminescence is only 1%.
Disclosure of Invention
In view of this, the present invention is directed to a dual-function integrated device for optical detection and electroluminescence, and a method for manufacturing the same, and an application of the same.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a light detection and electroluminescence dual-function integrated device which comprises a bottom electrode, an n-type semiconductor layer arranged on the upper surface of the bottom electrode, an i-type intermediate layer arranged on the upper surface of the n-type semiconductor layer, a p-type semiconductor layer arranged on the upper surface of the i-type intermediate layer and a top electrode arranged on the upper surface of the p-type semiconductor layer, wherein the n-type semiconductor layer is formed by ZnO microspheres, and the i-type intermediate layer is formed by CsPbBr3And forming the p-type semiconductor layer which is a GaN substrate doped with Mg.
Preferably, the thickness of the n-type semiconductor layer is 1.9-2.1 μm.
Preferably, the thickness of the i-type intermediate layer is 0.9-1.1 μm.
The invention provides a preparation method of the bifunctional integrated device in the technical scheme, which comprises the following steps:
(1) preparing ZnO microspheres on the upper surface of the bottom electrode, and annealing to form an n-type semiconductor layer;
(2) preparing CsPbBr on the upper surface of the n-type semiconductor layer in the step (1)3Forming an i-type interlayer through annealing treatment;
(3) arranging an Mg-doped GaN substrate on the upper surface of the i-type middle layer in the step (2), and packaging to obtain the dual-function integrated device; and a top electrode is arranged on the upper surface of the Mg-doped GaN substrate in advance.
Preferably, the method for preparing the ZnO microspheres in step (1) comprises the following steps:
mixing zinc salt, hexamethylenetetramine, sodium citrate dihydrate and water to obtain a precursor solution;
and immersing the precursor solution into a bottom electrode, preserving the heat for 1.5-2.5 h under the condition that the water bath temperature is 85-95 ℃, and preparing the ZnO microspheres on the upper surface of the bottom electrode.
Preferably, the temperature of the annealing treatment in the step (1) is 250-350 ℃, and the time of the annealing treatment is 1.5-2.5 h.
Preferably, CsPbBr is prepared in the step (2)3The method comprises the following steps:
coating PbBr on the upper surface of the n-type semiconductor layer in the step (1)2Baking the dimethyl sulfoxide solution, soaking the dimethyl sulfoxide solution in CsBr methanol solution for chemical combination reaction, and preparing CsPbBr on the upper surface of the n-type semiconductor layer3。
Preferably, the temperature of the combination reaction is 20-40 ℃, and the time of the combination reaction is 8-12 min.
Preferably, the temperature of the annealing treatment in the step (2) is 250-350 ℃, and the time of the annealing treatment is 8-12 min.
The invention provides application of the bifunctional integrated device in the technical scheme or the bifunctional integrated device prepared by the preparation method in the technical scheme in large-scale parallel data communication among an ultraviolet alarm integrated chip, an intelligent lighting lamp, an optical fiber communication repeater integrated element, a non-contact interactive display screen or a plurality of displays.
The invention provides a light detection and electroluminescence dual-function integrated device which comprises a bottom electrode, an n-type semiconductor layer arranged on the upper surface of the bottom electrode, an i-type intermediate layer arranged on the upper surface of the n-type semiconductor layer, a p-type semiconductor layer arranged on the upper surface of the i-type intermediate layer and a top electrode arranged on the upper surface of the p-type semiconductor layer, wherein the n-type semiconductor layer is formed by ZnO microspheres, and the i-type intermediate layer is formed by CsPbBr3And forming the p-type semiconductor layer which is a GaN substrate doped with Mg. The invention skillfully utilizes the energy level characteristics of the material and CsPbBr3The double carrier transport property of (inorganic perovskite) is that ZnO micron spheres are used as active layers in the absence of external bias (light detection mode), CsPbBr3And the Mg-doped GaN substrate is used as a hole transport layer, so that high-responsivity ultraviolet detection is realized; using CsPbBr3Excellent luminescence characteristics and ultra-high defect tolerance, and ZnO microspheres are used as an electron injection layer when a forward bias is applied externally (electroluminescence mode), CsPbBr3As active layer, Mg-doped GaN is usedFor the hole injection layer, ultra-pure green emission is achieved. The invention utilizes the separation of the active layers for light emission and detection, obtains the dual-function integrated device with different electroluminescent areas and light response wave bands for the first time, and effectively avoids the mutual reduction of the light emission and detection performances. The experimental results of the examples show that in the absence of external bias, the self-powered ultraviolet detection is realized by separating excitons in ZnO by utilizing the photovoltaic characteristics of the heterojunction, and the responsivity and the detection degree are respectively 0.23A/W and 2.4 multiplied by 1013cmHz1/2W; under forward bias, excitons are CsPbBr3And (4) the ultra-pure green light emission is realized through the intermediate recombination.
Furthermore, the dual-function integrated device provided by the invention can be used for preparing practical devices such as an ultraviolet alarm integrated chip, an intelligent lighting lamp and an optical fiber communication repeater integrated element, and can be applied to the fields of large-scale parallel data communication among a non-contact interactive display screen and a plurality of displays and the like.
Furthermore, compared with a single-performance discrete device, the dual-function integrated device provided by the invention has the advantages that the manufacturing time is reduced, the manufacturing cost is saved, the integration level is effectively improved, and the application potential is huge.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is an SEM image of the deposition of ZnO microspheres prepared from different concentrations of the precursor solution in example 1;
FIG. 2 shows different concentrations of PbBr in example 22CsPbBr prepared from dimethyl sulfoxide solution3SEM picture of (1);
FIG. 3 shows 1mol/L PbBr in example 22CsPbBr prepared from dimethyl sulfoxide solution3XRD pattern of (a);
fig. 4 is a diagram showing the structure and operation mode of the dual function integrated device in embodiment 3;
FIG. 5 is a characteristic curve of the photoelectric response I-V of the dual function integrated device in example 3;
FIG. 6 is the I-T characteristic curve of the photoelectric response of the dual function integrated device in example 3;
FIG. 7 is an electroluminescent I-V characteristic curve of the dual function integrated device of example 3;
FIG. 8 is an object diagram of electroluminescence of the dual function integrated device in example 3;
fig. 9 shows the electroluminescence lines of the dual function integrated device in example 3.
Detailed Description
The invention provides a light detection and electroluminescence dual-function integrated device which comprises a bottom electrode, an n-type semiconductor layer arranged on the upper surface of the bottom electrode, an i-type intermediate layer arranged on the upper surface of the n-type semiconductor layer, a p-type semiconductor layer arranged on the upper surface of the i-type intermediate layer and a top electrode arranged on the upper surface of the p-type semiconductor layer, wherein the n-type semiconductor layer is formed by ZnO microspheres, and the i-type intermediate layer is formed by CsPbBr3And forming the p-type semiconductor layer which is a GaN substrate doped with Mg.
The dual function integrated device provided by the invention comprises a bottom electrode. The bottom electrode is not particularly limited in the invention, and a bottom electrode well known to those skilled in the art can be adopted; in the embodiment of the invention, FTO conductive glass with the thickness of 380nm is particularly adopted as the bottom electrode.
The dual-function integrated device provided by the invention comprises an n-type semiconductor layer arranged on the upper surface of a bottom electrode, wherein the n-type semiconductor layer is formed by ZnO microspheres. In the present invention, the thickness of the n-type semiconductor layer is preferably 1.9 to 2.1 μm, and more preferably 2 μm. In the invention, during the process of preparing the ZnO microspheres on the upper surface of the bottom electrode, a layer of ZnO nano wall is firstly generated on the upper surface of the bottom electrode, and then the ZnO microspheres are generated on the ZnO nano wall; the thickness of the ZnO nano wall is preferably 400-600 nm, and more preferably 500 nm; the particle size of the ZnO microspheres is preferably 1.4-1.6 μm, and more preferably 1.5 μm.
The dual-function integrated device comprises an i-type intermediate layer arranged on the upper surface of the n-type semiconductor layer, wherein the i-type intermediate layer is made of CsPbBr3(all-inorganic perovskite). In the present invention, the thickness of the i-type intermediate layer is preferably 0.9 to 1.1 μm, and more preferably 1 μm. In bookIn the invention, the CsPbBr3The i-type intermediate layer is a recombination luminescence center of carriers.
The dual-function integrated device provided by the invention comprises a p-type semiconductor layer arranged on the upper surface of the i-type intermediate layer, wherein the p-type semiconductor layer is a GaN substrate doped with Mg. In the present invention, the Mg-doped GaN substrate preferably includes a substrate and an epitaxial layer on the substrate, the epitaxial layer being formed of Mg-doped GaN; the thickness of the epitaxial layer is preferably 3.9-4.1 μm, and more preferably 4 μm. In the present invention, the substrate is preferably a sapphire substrate. In the invention, the upper surface of the i-type interlayer in the dual-function integrated device is connected with the epitaxial layer of the Mg-doped GaN substrate.
The dual function integrated device provided by the invention comprises a top electrode arranged on the upper surface of the p-type semiconductor layer. The top electrode is not particularly limited in the invention, and the top electrode known to those skilled in the art can be adopted; in an embodiment of the invention, in particular an indium top electrode is used.
The invention provides a preparation method of the bifunctional integrated device in the technical scheme, which comprises the following steps:
(1) preparing ZnO microspheres on the upper surface of the bottom electrode, and annealing to form an n-type semiconductor layer;
(2) preparing CsPbBr on the upper surface of the n-type semiconductor layer in the step (1)3Forming an i-type interlayer through annealing treatment;
(3) arranging an Mg-doped GaN substrate on the upper surface of the i-type middle layer in the step (2), and packaging to obtain the dual-function integrated device; and a top electrode is arranged on the upper surface of the Mg-doped GaN substrate in advance.
The invention prepares ZnO microspheres on the upper surface of the bottom electrode, and forms an n-type semiconductor layer through annealing treatment. The invention preferably carries out pretreatment on the bottom electrode before use, and the pretreatment method preferably comprises washing treatment and ultraviolet ozone environment treatment which are sequentially carried out. In the invention, the washing treatment preferably comprises deionized water washing, acetone washing and ethanol washing which are sequentially carried out; the washing treatment is preferably carried out under ultrasonic conditions. In the embodiment of the invention, specifically, under the ultrasonic condition, the FTO conductive glass is washed for 15min by sequentially adopting deionized water, acetone and ethanol. In the invention, the washing treatment can remove impurities adsorbed on the surface of the FTO conductive glass, and the cleanliness of the FTO conductive glass is ensured. In the invention, the time of the ultraviolet ozone environment treatment is preferably 25-35 min; the ultraviolet ozone environment treatment is preferably carried out by adopting a Novascan PSD series ultraviolet ozone cleaning instrument. In the invention, the ultraviolet ozone environment treatment can increase the wettability of the surface of the FTO conductive glass.
In the present invention, the method for preparing the ZnO microspheres preferably comprises the steps of:
mixing zinc salt, hexamethylenetetramine, sodium citrate dihydrate and water to obtain a precursor solution;
and immersing the precursor solution into a bottom electrode, preserving the heat for 1.5-2.5 h under the condition that the water bath temperature is 85-95 ℃, and preparing the ZnO microspheres on the upper surface of the bottom electrode.
According to the invention, zinc salt, hexamethylenetetramine, sodium citrate dihydrate and water are preferably mixed to obtain the precursor solution. In the present invention, the molar ratio of the zinc salt, hexamethylenetetramine, sodium citrate dihydrate and the volume ratio of water is preferably 3 mmol: (2.8-3.2) mmol: (0.75 to 0.85) mmol: (280-320) mL; more preferably 3 mmol: 3 mmol: 0.8 mmol: 300 mL. In the present invention, the zinc salt preferably includes zinc nitrate hexahydrate or zinc acetate. In the present invention, the mixing of the zinc salt, hexamethylenetetramine, sodium citrate dihydrate and water is preferably performed under stirring conditions; the stirring is not specially limited, and the zinc salt, the hexamethylenetetramine and the sodium citrate dihydrate can be completely dissolved in water to uniformly mix the materials.
After the precursor solution is obtained, the invention preferably immerses the precursor solution in a bottom electrode, keeps the temperature for 1.5-2.5 h under the condition that the water bath temperature is 85-95 ℃, and prepares the ZnO microspheres on the upper surface of the bottom electrode. In the embodiment of the invention, during laboratory tests, the precursor solution is poured into a beaker with a bottom electrode laid at the bottom, the bottom electrode is immersed, and then the beaker is placed in a water bath at 85-95 ℃ and is kept warm for 1.5-2.5 h. In the invention, the pouring of the precursor liquid into the beaker with the bottom electrode paved at the bottom needs to be carried out slowly, so that the bottom electrode paved at the bottom of the beaker is prevented from being overturned due to too fast pouring.
After the heat preservation is finished, the obtained sample wafer is preferably washed and dried in sequence. In the present invention, the washing reagent used for the washing is preferably deionized water. In the present invention, the drying is preferably performed under a protective atmosphere; the drying temperature is preferably 75-85 ℃, and the drying time is preferably 1.5-2.5 h. The protective gas for providing the protective atmosphere is not particularly limited in the present invention, and a protective gas known to those skilled in the art, such as nitrogen, may be used. In the present invention, the drying is for removing the washing agent remaining after the washing.
After preparing the ZnO microspheres on the upper surface of the bottom electrode, the invention forms an n-type semiconductor layer on the upper surface of the bottom electrode by annealing the obtained sample wafer. In the invention, the annealing treatment temperature is preferably 250-350 ℃, more preferably 275-325 ℃, and most preferably 300 ℃; the time of the annealing treatment is preferably 1.5-2.5 h, and more preferably 2 h. The equipment used for carrying out the annealing treatment in the present invention is not particularly limited, and equipment capable of carrying out the annealing treatment, which is well known to those skilled in the art, such as a muffle furnace, may be used. In the invention, the annealing treatment can improve the crystallinity of the ZnO microspheres and reduce oxygen vacancies.
After an n-type semiconductor layer is formed on the upper surface of the bottom electrode, CsPbBr is prepared on the upper surface of the n-type semiconductor layer3And forming an i-type intermediate layer through annealing treatment. In the present invention, the CsPbBr is prepared3Preferably the method of (a) comprises the steps of:
coating PbBr on the upper surface of the n-type semiconductor layer2Baking the dimethyl sulfoxide solution, soaking the dimethyl sulfoxide solution in CsBr methanol solution for chemical combination reaction, and preparing CsPbBr on the upper surface of the n-type semiconductor layer3。
In the present inventionThe PbBr is2The concentration of the dimethyl sulfoxide solution is preferably 0.8-1.2 mmol/mL, and more preferably 1 mmol/mL. In the present invention, the PbBr is2The preferable preparation method of dimethyl maple solution is that PbBr is added2Mixing with dimethyl sulfoxide, and keeping the temperature at 65-75 ℃ for 14-16 h to ensure that PbBr is added2Fully dissolving in dimethyl sulfoxide to form colloid; filtering the colloid by a filter screen with the aperture of 0.22 mu m to remove PbBr with larger particle size2Granulation to obtain PbBr2Dimethyl sulfoxide solution.
The coating is not particularly limited in the invention, and the technical scheme of coating known to those skilled in the art can be adopted; in the embodiment of the invention, spin coating is specifically adopted; the rotation speed of the spin coating is preferably 2800-3200 rpm, and the time of the spin coating is preferably 25-35 s.
In the invention, the baking treatment temperature is preferably 75-85 ℃, and the baking treatment time is preferably 25-35 min. In the present invention, the baking treatment is for removing dimethyl sulfoxide.
In the invention, the concentration of the CsBr methanol solution is preferably 13-17 mg/mL, and more preferably 15 mg/mL. In the invention, the preparation method of the CsBr methanol solution is preferably to mix CsBr and methanol and stir for 25-35 min to fully dissolve CsBr in the methanol.
In the invention, the temperature of the combination reaction is preferably 20-40 ℃, and more preferably 25-35 ℃; in the examples of the present invention, the combination reaction is specifically carried out at room temperature, i.e. without additional heating or cooling. In the invention, the time of the combination reaction is preferably 8-12 min, and more preferably 10 min.
Preparing CsPbBr on the upper surface of the n-type semiconductor layer3And then, annealing the obtained sample wafer to form an i-type intermediate layer on the upper surface of the n-type semiconductor layer. In the invention, the annealing treatment temperature is preferably 250-350 ℃, more preferably 275-325 ℃, and most preferably 300 ℃; the time of the annealing treatment is preferably 8-12 min, and more preferably 10 min. The invention does not have equipment for carrying out the annealing treatmentThe annealing treatment may be carried out by any equipment known to those skilled in the art, specifically, a hot stage. In the invention, the annealing treatment can remove residual dimethyl sulfoxide and improve CsPbBr3The crystallinity of (a).
After an i-type middle layer is formed on the upper surface of the n-type semiconductor layer, arranging an Mg-doped GaN substrate on the upper surface of the i-type middle layer, and packaging to obtain the dual-function integrated device; and a top electrode is arranged on the upper surface of the Mg-doped GaN substrate in advance. In the present invention, a method of providing a top electrode on the upper surface of the Mg-doped GaN substrate in advance, preferably, molten indium is coated on the upper surface of the Mg-doped GaN substrate; the molten indium is preferably obtained by melting indium particles using an electric iron.
The present invention is not limited to the above-mentioned packaging process, and a technical solution of the packaging process known to those skilled in the art may be adopted. In the embodiment of the invention, indium particles are melted by using an electric soldering iron and then coated on the upper surface of the Mg-doped GaN substrate, and the lower surface of the Mg-doped GaN substrate is aligned to the i-type middle layer to form a cross shape, so that both a bottom electrode and a top electrode can be exposed outside, and the test is convenient; fixing the Mg-doped GaN substrate with the top electrode pre-arranged on the upper surface and a sample wafer with an i-type intermediate layer by using a clamp so as to prevent the Mg-doped GaN substrate and the sample wafer from sliding in the subsequent packaging process; and finally, filling the Mg-doped GaN substrate with the top electrode pre-arranged on the upper surface and the sample wafer with the i-type middle layer with epoxy resin glue to form a whole (attention needs to be paid to avoid the situation that the epoxy resin glue enters the interface between the two layers of materials to influence the performance of the device), and taking down the clamp after the epoxy resin glue is dried and solidified to obtain the dual-function integrated device.
The invention provides application of the bifunctional integrated device in the technical scheme or the bifunctional integrated device prepared by the preparation method in the technical scheme in large-scale parallel data communication among an ultraviolet alarm integrated chip, an intelligent lighting lamp, an optical fiber communication repeater integrated element, a non-contact interactive display screen or a plurality of displays.
In the invention, the dual-function integrated device can be applied to an ultraviolet alarm integrated chip. Excessive uv radiation can cause serious health problems such as skin cancer, but the human eye cannot observe uv light. Under the assistance of an external circuit, the dual-function integrated device provided by the invention is used for detecting ultraviolet rays, and the working mode is as follows: when the ultraviolet ray exceeds the standard, an external circuit supplies a high voltage to enable the dual-function integrated device to emit green light; if the ultraviolet ray does not exceed the standard, the external circuit supplies a low voltage, and the dual-function integrated device continues to detect the ultraviolet ray. The light emitted by the dual-function integrated device provided by the invention is just in a green light waveband, and the waveband is the most sensitive region of human eyes, which is the advantage of the dual-function integrated device provided by the invention. In the invention, the ultraviolet alarm integrated chip can be used as a detachable part of a smart phone or a watch.
In the invention, the dual-function integrated device can be applied to an intelligent lighting lamp. Under the assistance of an external circuit, the dual-function integrated device provided by the invention controls the luminous intensity of the intelligent lighting lamp through the detected light intensity, and the working mode is as follows: in the daytime, the stronger the ambient light is, the larger the photocurrent output by the dual-function integrated device is, the smaller the voltage fed back to the dual-function integrated device by an external circuit is, and the weaker the light-emitting brightness of the dual-function integrated device is; on the contrary, at night, the weaker the ambient light is, the smaller the photocurrent output by the dual-function integrated device is, the larger the voltage fed back to the dual-function integrated device by an external circuit is, and the stronger the light-emitting brightness of the dual-function integrated device is. The intensity of the brightness of the intelligent lighting lamp is inversely proportional to the intensity of the ambient light, the function of regulating and controlling the ambient brightness in real time is achieved, and the comfort level of the living environment is ensured.
In the invention, the dual-function integrated device can be applied to an integrated element of a fiber-optic communication repeater. In fiber optic communications, repeaters function to retransmit or forward data signals. The dual-function integrated device provided by the invention can realize two functions of receiving and sending signals, so that the dual-function integrated device can realize at least twice of the performance of a single performance separation device on the same integration level. At least more than two bifunctional integrated devices provided by the invention can be manufactured in the volume of manufacturing one photoelectric detector and one heterojunction laser, so that the preparation cost is greatly reduced, and the cost performance is increased.
In the invention, the dual function integrated device can be applied to a non-contact interactive display screen. The dual-function integrated device provided by the invention can be used as a pixel point of a display screen, and the intensity of light emission is controlled by detecting the intensity of light with the assistance of an external circuit, and the working mode is as follows: when the finger is close to the display screen, the ambient light is shielded, so that the light intensity of the display screen is weaker than that of other areas, and the touch positioning can be realized; meanwhile, an external circuit detects a small photocurrent and feeds back a small voltage to the dual-function integrated device, so that the light emission is weakened. Therefore, the closer the finger is to the display screen, the lower the detected light intensity is, and the weaker the pixel point emits light. On the contrary, the farther the finger is away from the display screen, the stronger the detected light intensity is, and the stronger the pixel point is. From the inherent light intensity setting of the traditional human passive display screen to the active interaction of the existing real-time human-computer interaction, the light intensity display which is customized to meet the specific habit of the user is realized.
In the invention, the dual-function integrated device can be applied to massive parallel data communication among a plurality of displays. In the background of the era of big data, the demand of ultra-high speed transmission of data is increasingly strong. The display prepared by the dual-function integrated device provided by the invention can well solve the problem of ultra-high speed transmission of face-to-face short-distance data. Specifically, a display is operated in an electroluminescence mode and used as a data transmitting end; the other display is operated in a light detection mode as a data receiving end. The advantage of extremely high integration level of the display (hundreds of millions of pixel points are integrated in unit area) is ingeniously utilized, and therefore the function of large-scale parallel data communication is achieved. Specifically, the dual-function integrated device provided by the invention is used as pixel points, one pixel point transmits, the other pixel point receives, and when hundreds of millions of pixel points simultaneously transmit and receive, large-scale parallel data communication can be easily realized.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples of the invention, field emission Scanning Electron Microscopy (SEM) (JSM-7100F) and X-ray diffraction (XRD) (Bruker D8 advanced CuKa radiation) were used to characterize the ZnO microspheres and CsPbBr3Morphology and crystal structure of; adopting Agilent B1500a to test the photoelectric performance of the dual-function integrated device; the electroluminescence line of the bifunctional integrated device was measured using PrincetonInstruments Acton SP 2500.
Example 1
(1) Sequentially ultrasonically washing the FTO conductive glass for 15min by using deionized water, acetone and ethanol, and then treating the FTO conductive glass for 30min in an ultraviolet ozone environment to obtain FTO conductive glass as a bottom electrode;
(2) 0.8924g of zinc nitrate hexahydrate, 0.4206g of hexamethylenetetramine and 0.2240g of sodium citrate dihydrate are dissolved in 50mL of deionized water, and the mixture is stirred for 15min until the mixture is fully dissolved; respectively adding 200mL, 250mL, 300mL and 350mL of deionized water to obtain precursor solutions diluted by 5 times, 6 times, 7 times and 8 times;
(3) slowly pouring the precursor solutions into beakers with bottom electrodes laid at the bottoms respectively, immersing the bottom electrodes, then placing the beakers in a water bath, and keeping the temperature at 90 ℃ for 2 hours; and taking out the obtained sample wafer, washing with deionized water, drying at 80 ℃ for 2h in a nitrogen atmosphere, finally annealing at 300 ℃ for 2h in a muffle furnace, and forming a ZnO microsphere n-type semiconductor layer prepared from precursor solutions with different concentrations on the upper surface of the bottom electrode.
And performing SEM characterization analysis on the ZnO microspheres prepared from the obtained precursor solutions with different concentrations, wherein the result is shown in figure 1. FIG. 1 is an SEM image of the deposition of ZnO microspheres prepared from different concentrations of the precursor solution, wherein (a), (b), (c) and (d) correspond to the dilution factors of the precursor solution of 5,6, 7 and 8 times in sequence. As can be seen from fig. 1, as the dilution factor increases, the concentration of the precursor solution decreases, the number of ZnO microspheres grown using the precursor solution decreases, the distribution becomes sparse, and the thickness decreases from a plurality of layers to one layer.
Example 2
(1) Sequentially ultrasonically washing the FTO conductive glass for 15min by using deionized water, acetone and ethanol, and then treating the FTO conductive glass for 30min in an ultraviolet ozone environment to obtain FTO conductive glass as a bottom electrode;
(2) 0.8924g of zinc nitrate hexahydrate, 0.4206g of hexamethylenetetramine and 0.2240g of sodium citrate dihydrate are dissolved in 300mL of deionized water, and the mixture is stirred for 15min until the mixture is fully dissolved to obtain a precursor solution; slowly pouring the precursor solution into a beaker with a bottom electrode laid at the bottom, immersing the bottom electrode, then placing the beaker in a water bath, and keeping the temperature at 90 ℃ for 2 hours; taking out the obtained sample wafer, washing with deionized water, drying in a nitrogen atmosphere at 80 ℃ for 2h, finally annealing in a muffle furnace at 300 ℃ for 2h, and forming a ZnO micron spherical n-type semiconductor layer on the upper surface of the bottom electrode;
(3) adding 0.5mmol, 0.75mmol, 1mmol, 1.25mmol and 1.5mmol of PbBr2Dissolving in 1mL of dimethyl sulfoxide, and keeping the temperature at 70 ℃ for 15h to make PbBr2Fully dissolving to form colloid, filtering with a filter screen with pore diameter of 0.22 μm, and removing PbBr with large particle diameter2Granulating to obtain PbBr with different concentrations2Dimethyl sulfoxide solution;
(3) dissolving 0.3g CsBr in 20mL of methanol, and stirring for 30min to obtain a CsBr methanol solution; reacting PbBr2Respectively spin-coating a dimethyl sulfoxide solution on the upper surface of an n-type semiconductor layer (the spin-coating speed is 3000rpm, the spin-coating time is 30s), baking at 80 ℃ for 30min, soaking in a CsBr methanol solution for 10min, annealing at 250 ℃ for 10min, and forming PbBr with different concentrations on the upper surface of the n-type semiconductor layer2CsPbBr prepared from dimethyl sulfoxide solution3An i-type interlayer.
The obtained PbBr with different concentrations2CsPbBr prepared from dimethyl sulfoxide solution3SEM characterization was performed as follows:
FIG. 2 shows different concentrations of PbBr2CsPbBr prepared from dimethyl sulfoxide solution3In FIG. 2, the SEM pictures of (a) to (e) are 0.5mol/L, 0.75mol/L, 1mol/L, 1.25mol/L and 1.5mol/L PbBr in sequence2CsPbBr prepared from dimethyl sulfoxide solution3A surface topography map of; (f) is 1mol/L PbBr2CsPbBr prepared from dimethyl sulfoxide solution3Cross-sectional topography of (a). As can be seen from comparison of FIGS. 2(a) to (e), only 1mol/L of PbBr was observed2The dimethyl sulfoxide solution can prepare more continuous CsPbBr without other obvious defects3(ii) a As can be seen from FIG. 2(f), CsPbBr3The ZnO microspheres are uniformly wrapped.
FIG. 3 shows 1mol/LPbBr2CsPbBr prepared from dimethyl sulfoxide solution3XRD pattern of (a). From the analysis of FIG. 3, it can be seen that CsPbBr is present in the sample3Has no other impurities; and the CsPbBr3Belonging to the cubic phase.
Example 3
(1) Sequentially ultrasonically washing the FTO conductive glass for 15min by using deionized water, acetone and ethanol, and then treating the FTO conductive glass for 30min in an ultraviolet ozone environment to obtain FTO conductive glass as a bottom electrode;
(2) 0.8924g of zinc nitrate hexahydrate, 0.4206g of hexamethylenetetramine and 0.2240g of sodium citrate dihydrate are dissolved in 300mL of deionized water, and the mixture is stirred for 15min until the mixture is fully dissolved to obtain a precursor solution; slowly pouring the precursor solution into a beaker with a bottom electrode laid at the bottom, immersing the bottom electrode, then placing the beaker in a water bath, and keeping the temperature at 90 ℃ for 2 hours; taking out the obtained sample wafer, washing with deionized water, drying in a nitrogen atmosphere at 80 ℃ for 2h, finally annealing in a muffle furnace at 300 ℃ for 2h, and forming a ZnO micron spherical n-type semiconductor layer on the upper surface of the bottom electrode;
(3) 1mmol of PbBr2Dissolving in 1mL dimethyl sulfoxide, and keeping the temperature at 70 ℃ for 15h to ensure that PbBr is added2Fully dissolving to form colloid, filtering with a filter screen with pore diameter of 0.22 μm, and removing PbBr with large particle diameter2Granulation to obtain PbBr2Dimethyl sulfoxide solution; dissolving 0.3g CsBr in 20mL of methanol, and stirring for 30min to obtain a CsBr methanol solution; reacting PbBr2Spin-coating dimethyl sulfoxide solution (the rotation speed of the spin-coating is 3000rpm, the spin-coating time is 30s) on the upper surface of the n-type semiconductor layer, baking at 80 ℃ for 30min, then soaking in CsBr methanol solution for 10min, annealing at 250 ℃ for 10min, and forming CsPbBr on the upper surface of the n-type semiconductor layer3An i-type interlayer;
(4) melting indium particles by using an electric soldering iron, coating the melted indium particles on the upper surface of the Mg-doped GaN substrate, and aligning the lower surface of the Mg-doped GaN substrate to the i-type middle layer to form a cross shape so as to ensure that both the bottom electrode and the top electrode can be exposed; fixing the Mg-doped GaN substrate with the top electrode pre-arranged on the upper surface and a sample wafer with an i-type intermediate layer by using a clamp; and finally, filling the Mg-doped GaN substrate with the top electrode pre-arranged on the upper surface and the sample wafer with the i-type middle layer with epoxy resin glue to form a whole, and taking down the clamp after the epoxy resin glue is dried and solidified to obtain the dual-function integrated device.
The bifunctional integrated device is subjected to light response performance and electroluminescence performance tests, and the results are as follows:
fig. 4 shows the structure and operation mode of the dual function integrated device. As can be seen from FIG. 4, the dual function integrated device comprises an FTO bottom electrode, a ZnO micro-sphere n-type semiconductor layer, and CsPbBr3An i-type interlayer, a GaN substrate p-type semiconductor layer doped with Mg and an indium top electrode, wherein the ZnO microsphere n-type semiconductor layer and CsPbBr3The i-type intermediate layer and the Mg-doped GaN substrate p-type semiconductor layer construct an nip heterojunction. In the absence of an external bias, ZnO is an absorption layer, excitons are separated in ZnO, CsPbBr3As a hole transport layer, the material shows super ultraviolet response. ZnO acts as an electron injection layer, CsPbBr, when a forward bias is externally applied3As an active layer, excitons in CsPbBr3The green light is compounded to emit ultra-pure green light. In both modes, GaN is acting to transport holes.
Fig. 5 is a photoelectric response I-V characteristic curve of the dual function integrated device. As can be seen from fig. 5, by comparing the current values under the same bias voltage with the light and dark conditions, the difference of the current values is found to be the largest under the condition of no applied bias voltage (0V). It can be seen that the dual function integrated device exhibits good self-powered optical probing behavior.
Fig. 6 is a photoelectric response I-T characteristic curve of the dual function integrated device. As can be seen from fig. 6, under the condition of no external bias, the current value of the dual-function integrated device can be observed to follow the periodic variation of illumination. After 4 cycles, no significant attenuation of the maximum current value is found, which proves that the dual-function integrated device has better stability in light detection. In addition, the maximum current values found for devices with nip structures were significantly stronger than those of np structures, indicating the insertion of CsPbBr3The transmission efficiency of the holes is enhanced, and the optical detection is facilitated.
Fig. 7 is an electroluminescent I-V characteristic curve of the dual function integrated device. As can be seen from fig. 7, the dual function integrated device exhibits good rectification characteristics.
Fig. 8 is a diagram of a light-emitting object of the dual function integrated device, a cluster of green light can be easily observed.
Fig. 9 shows the electroluminescence lines of the dual function integrated device. As can be seen from FIG. 9, when the applied bias voltage is 24V, the light emission curve is centered around 529nm and is green, and no light emission peak is observed in other regions; and the half-width of the luminescence peak is only 19.2 nm. This indicates that the dual function integrated device has a high luminescent purity.
From the above examples, the present invention skillfully utilizes the energy level characteristics of the material and CsPbBr3The double carrier transport property of (inorganic perovskite) is that ZnO micron spheres are used as active layers in the absence of external bias (light detection mode), CsPbBr3And the Mg-doped GaN substrate is used as a hole transport layer, so that high-responsivity ultraviolet detection is realized; using CsPbBr3Excellent luminescence characteristics and ultra-high defect tolerance, and ZnO microspheres are used as an electron injection layer when a forward bias is applied externally (electroluminescence mode), CsPbBr3As an active layer, Mg doped GaN as a hole injection layer, ultra pure green emission was achieved. The invention utilizes luminescence and detectionThe active layer is separated, the dual-function integrated device with different electroluminescent areas and different light response wave bands is obtained for the first time, the mutual reduction of the luminescence and detection performances is effectively avoided, and the method has huge application potential.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A light detection and electroluminescence dual-function integrated device comprises a bottom electrode, an n-type semiconductor layer arranged on the upper surface of the bottom electrode, an i-type intermediate layer arranged on the upper surface of the n-type semiconductor layer, a p-type semiconductor layer arranged on the upper surface of the i-type intermediate layer and a top electrode arranged on the upper surface of the p-type semiconductor layer, wherein the n-type semiconductor layer is formed by ZnO microspheres, and the i-type intermediate layer is formed by CsPbBr3And forming the p-type semiconductor layer which is a GaN substrate doped with Mg.
2. The bifunctional integrated device according to claim 1, wherein the n-type semiconductor layer has a thickness of 1.9-2.1 μm.
3. The bifunctional integrated device according to claim 1, wherein the thickness of the i-type interlayer is 0.9-1.1 μm.
4. A method for preparing a bifunctional integrated device as defined in any of claims 1 to 3, comprising the steps of:
(1) preparing ZnO microspheres on the upper surface of the bottom electrode, and annealing to form an n-type semiconductor layer;
(2) preparing CsPbBr on the upper surface of the n-type semiconductor layer in the step (1)3Forming an i-type interlayer through annealing treatment;
(3) arranging an Mg-doped GaN substrate on the upper surface of the i-type middle layer in the step (2), and packaging to obtain the dual-function integrated device; and a top electrode is arranged on the upper surface of the Mg-doped GaN substrate in advance.
5. The preparation method according to claim 4, wherein the method for preparing ZnO microspheres in the step (1) comprises the following steps:
mixing zinc salt, hexamethylenetetramine, sodium citrate dihydrate and water to obtain a precursor solution;
and immersing the precursor solution into a bottom electrode, preserving the heat for 1.5-2.5 h under the condition that the water bath temperature is 85-95 ℃, and preparing the ZnO microspheres on the upper surface of the bottom electrode.
6. The preparation method according to claim 4 or 5, wherein the temperature of the annealing treatment in the step (1) is 250-350 ℃, and the time of the annealing treatment is 1.5-2.5 h.
7. The production method according to claim 4, wherein CsPbBr is produced in the step (2)3The method comprises the following steps:
coating PbBr on the upper surface of the n-type semiconductor layer in the step (1)2Baking the dimethyl sulfoxide solution, soaking the dimethyl sulfoxide solution in CsBr methanol solution for chemical combination reaction, and preparing CsPbBr on the upper surface of the n-type semiconductor layer3。
8. The preparation method according to claim 7, wherein the temperature of the combination reaction is 20-40 ℃, and the time of the combination reaction is 8-12 min.
9. The method according to claim 4, 7 or 8, wherein the temperature of the annealing treatment in the step (2) is 250 to 350 ℃, and the time of the annealing treatment is 8 to 12 min.
10. Use of the bifunctional integrated device according to any one of claims 1 to 3 or the bifunctional integrated device prepared by the preparation method according to any one of claims 4 to 9 in an integrated chip of an ultraviolet alarm, an intelligent lighting fixture, an integrated component of an optical fiber communication repeater, a non-contact interactive display screen or a large-scale parallel data communication among a plurality of displays.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810166532.0A CN108198814B (en) | 2018-02-28 | 2018-02-28 | Optical detection and electroluminescence dual-function integrated device and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810166532.0A CN108198814B (en) | 2018-02-28 | 2018-02-28 | Optical detection and electroluminescence dual-function integrated device and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108198814A CN108198814A (en) | 2018-06-22 |
| CN108198814B true CN108198814B (en) | 2020-04-10 |
Family
ID=62594518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810166532.0A Active CN108198814B (en) | 2018-02-28 | 2018-02-28 | Optical detection and electroluminescence dual-function integrated device and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108198814B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108987601B (en) * | 2018-07-26 | 2020-11-03 | 京东方科技集团股份有限公司 | Diode device, manufacturing method thereof and diode device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101170146A (en) * | 2006-10-27 | 2008-04-30 | 中国科学院物理研究所 | An optical detector with full wave length and its making method |
| CN106229424A (en) * | 2016-08-23 | 2016-12-14 | 陕西师范大学 | A kind of luminescent device based on perovskite thin slice and preparation method thereof |
| CN106450009A (en) * | 2016-08-05 | 2017-02-22 | 苏州大学 | Double-layer perovskite light-emitting diode and preparation method thereof |
| CN208045499U (en) * | 2018-02-28 | 2018-11-02 | 湖北大学 | A kind of optical detection and the difunctional integrated device of electroluminescent |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100276731A1 (en) * | 2009-05-04 | 2010-11-04 | Brookhaven Science Associates, Llc. | Inorganic Nanocrystal Bulk Heterojunctions |
-
2018
- 2018-02-28 CN CN201810166532.0A patent/CN108198814B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101170146A (en) * | 2006-10-27 | 2008-04-30 | 中国科学院物理研究所 | An optical detector with full wave length and its making method |
| CN106450009A (en) * | 2016-08-05 | 2017-02-22 | 苏州大学 | Double-layer perovskite light-emitting diode and preparation method thereof |
| CN106229424A (en) * | 2016-08-23 | 2016-12-14 | 陕西师范大学 | A kind of luminescent device based on perovskite thin slice and preparation method thereof |
| CN208045499U (en) * | 2018-02-28 | 2018-11-02 | 湖北大学 | A kind of optical detection and the difunctional integrated device of electroluminescent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108198814A (en) | 2018-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | High-bandwidth InGaN self-powered detector arrays toward MIMO visible light communication based on micro-LED arrays | |
| Li et al. | One-step preparation of long-term stable and flexible CsPbBr3 perovskite quantum dots/ethylene vinyl acetate copolymer composite films for white light-emitting diodes | |
| US10749065B2 (en) | Preparation method and application of light-responsive LED based on GaN/CsPbBrxI3-x heterojunction | |
| Su et al. | Recent progress in quantum dot based white light-emitting devices | |
| CN104937722B (en) | Using the Intermediate Gray quasiconductor, hetero-junctions and the optoelectronic device that process quantum dot solution manufacture, and its correlation technique | |
| CN108251117B (en) | Core-shell quantum dot, preparation method thereof and electroluminescent device containing core-shell quantum dot | |
| Manousiadis et al. | Organic semiconductors for visible light communications | |
| CN111740033B (en) | Near-infrared perovskite light-emitting diode and preparation method thereof | |
| JP2021523530A (en) | Quantum dot LED design based on resonance energy transfer | |
| TWI613275B (en) | Quantum dot composite material and manufacturing method and application thereof | |
| TW201119082A (en) | Stable and all solution processable quantum dot light-emitting diodes | |
| Song et al. | All-inorganic perovskite CsPbBr 3-based self-powered light-emitting photodetectors with ZnO hollow balls as an ultraviolet response center | |
| CN102916097A (en) | Electroluminescent device | |
| CN103429701A (en) | Color stable manganese-doped phosphors | |
| TW200908411A (en) | Electroluminescent device having improved power distribution | |
| WO2011078467A2 (en) | Laser diode using zinc oxide nanorods and manufacturing method thereof | |
| Oh et al. | Down-conversion light outcoupling films using imprinted microlens arrays for white organic light-emitting diodes | |
| CN110943178A (en) | Self-assembly multi-dimensional quantum well CsPbX3Perovskite nanocrystalline electroluminescent diode | |
| Zhao et al. | Inorganic halide perovskites for lighting and visible light communication | |
| Yan et al. | Enhancing the performance of blue quantum-dot light-emitting diodes based on Mg-doped ZnO as an electron transport layer | |
| Yu et al. | Water-stable CsPbBr 3 perovskite quantum-dot luminous fibers fabricated by centrifugal spinning for dual white light illumination and communication | |
| Xue et al. | Enhanced bandwidth of white light communication using nanomaterial phosphors | |
| Demir et al. | White light generation tuned by dual hybridization of nanocrystals and conjugated polymers | |
| Lu et al. | High-speed visible light communication based on micro-LED: A technology with wide applications in next generation communication | |
| Wei et al. | Synthesis of emission tunable AgInS2/ZnS quantum dots and application for light emitting diodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |