CN111900253A - Novel perovskite-based heterojunction photoelectric device and preparation method thereof - Google Patents
Novel perovskite-based heterojunction photoelectric device and preparation method thereof Download PDFInfo
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- CN111900253A CN111900253A CN202010544794.3A CN202010544794A CN111900253A CN 111900253 A CN111900253 A CN 111900253A CN 202010544794 A CN202010544794 A CN 202010544794A CN 111900253 A CN111900253 A CN 111900253A
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- 239000010409 thin film Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 18
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 16
- 239000004065 semiconductor Substances 0.000 claims description 12
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 11
- 230000005693 optoelectronics Effects 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 239000000084 colloidal system Substances 0.000 claims description 7
- 238000002161 passivation Methods 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- 239000011241 protective layer Substances 0.000 claims description 5
- 238000000231 atomic layer deposition Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000005566 electron beam evaporation Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 description 10
- 238000011160 research Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 241000588731 Hafnia Species 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
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- 238000005424 photoluminescence Methods 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- 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
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- 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
- H01L31/10—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 characterised by at least one potential-jump barrier or surface barrier, e.g. phototransistors
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Abstract
The invention discloses a perovskite-based novel heterojunction photoelectric device and a preparation method thereof. The photoelectric device disclosed by the invention has the advantages of small volume, low cost, high performance, simple manufacture, high detection sensitivity and ultrahigh external quantum efficiency, and has great application potential in the field of photoelectric devices.
Description
Technical Field
The invention relates to a photoelectric device, in particular to a novel heterojunction photoelectric device based on perovskite and a preparation method thereof.
Background
Perovskite is one of the most popular materials in recent years, and a new round of research hot tide is successfully initiated. Various perovskite materials such as organic-inorganic hybrid perovskite, all-inorganic perovskite and the like attract the research interest of a plurality of researchers in the fields of photovoltaics, photoelectricity, thermoelectricity and the like, and the perovskite materials have simpler growth process and higher stability, so the perovskite materials are widely concerned. The quantum yield of partial perovskite is as high as 90%, and the partial perovskite has proper forbidden band width and narrow line width of Photoluminescence (PL) emission spectrum, so that the perovskite can be applied to the photoelectric field, such as solar cells, LEDs, photodetectors and the like. And the advantages of the photoelectric field are more obvious due to the lower carrier recombination speed.
Generally, the development of perovskites in the electronic field is influenced by the characteristics of perovskites, and the perovskites hardly have a considerable current value, so that the research on the photoelectric characteristics of corresponding devices is more difficult, and the detection degree and the External Quantum Efficiency (EQE) are poor, which greatly limits the research on perovskites in the field of phototransistors. Therefore, the development of a perovskite photoelectric device with high efficiency, sensitivity and low cost is of great significance.
At the same time, HfO2As an insulating material, recent research also has newly found in the photoelectric detection direction that at a relatively thin thickness, electrons can pass through HfO by tunneling effect2Layer and more outstanding results in photodetection are also achieved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a novel perovskite-based heterojunction photoelectric device and a preparation method thereof, so as to achieve the purposes of small volume, low cost, simple manufacture, high responsivity, low light detection limit and ultrahigh external quantum efficiency.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the utility model provides a novel heterojunction photoelectric device based on perovskite, includes semiconductor substrate and the hafnia layer that is located its upper surface, hafnia layer upper surface is equipped with source electrode and drain electrode, hafnia layer upper surface is located be equipped with the perovskite film between source electrode and the drain electrode, semiconductor substrate lower surface sets up the grid electrode.
In the scheme, a passivation protective layer is arranged on the upper surface of the perovskite thin film.
In the above scheme, the thickness of the hafnium oxide layer is 5-50 nm.
In the above scheme, the perovskite thin film is an organic perovskite material or an inorganic perovskite material.
In the above scheme, the perovskite thin film is obtained by a spin coating method or an epitaxial growth method.
A preparation method of a novel perovskite-based heterojunction photoelectric device comprises the following steps:
(1) growing a hafnium oxide layer on the surface of the semiconductor substrate by an atomic layer deposition method;
(2) designing the pattern of a source electrode and a drain electrode and the length of a channel through a mask, and depositing the source electrode and the drain electrode on the hafnium oxide layer in an electron beam evaporation mode;
(3) preparing a perovskite thin film on the hafnium oxide layer between the source electrode and the drain electrode by a spin coating method or an epitaxial growth method to form perovskite/HfO2A heterostructure photovoltaic device.
In a further technical scheme, after the perovskite thin film is obtained, a passivation protective layer is deposited on the upper surface of the perovskite thin film.
In the above scheme, the spin coating method specifically comprises the following steps: firstly, preparing perovskite colloid by a chemical synthesis method; and dripping the perovskite colloid on the surface of the hafnium oxide layer between the source electrode and the drain electrode, and drying to obtain the continuous perovskite thin film.
Through the technical scheme, the novel perovskite-based heterojunction photoelectric device and the preparation method thereof have the following beneficial effects:
(1) the invention realizes the manufacture of the photoelectric device with simple process;
(2) the invention utilizes the excellent photoelectronic characteristics of perovskite, and the prepared photoelectric device has high responsivity45A/W), low light detection limit (0.15. mu.W/cm)2) Ultra high EQE (12445 Jones);
(3) the invention utilizes HfO2The layer forms a heterojunction with the perovskite thin film and receives an optical signal, HfO2The layer can be used as a dielectric layer and has good tunneling effect, so that electrons can penetrate through HfO2The layer enables the device to have more prominent photoelectric correspondence under different illumination powers;
(4) the photoelectric device has the advantages of small volume, low cost, high performance, simple manufacture and high detection sensitivity, and has great application potential in the field of photoelectric devices.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a schematic diagram of a novel perovskite-based heterojunction optoelectronic device disclosed in an embodiment of the present invention;
FIG. 2 is a schematic diagram of a novel perovskite-based heterojunction optoelectronic device disclosed in the second embodiment of the present invention;
FIG. 3 is a circuit diagram of a disclosed optoelectronic device in accordance with one embodiment of the present invention;
FIG. 4a shows a view of a disclosed optoelectronic device at V according to an embodiment of the present inventiongsDark current and photocurrent contrast plots at 0V;
FIG. 4b illustrates the photovoltaic device disclosed in an embodiment of the present invention at VdsDark current and photocurrent contrast plots at 0V;
FIG. 5 is a diagram illustrating the magnitude of photocurrent of the optoelectronic device under different illumination powers at a wavelength of 450 nm;
fig. 6 is a graph showing the change of detectivity (D), responsivity (R) and External Quantum Efficiency (EQE) of the optoelectronic device at different optical powers.
In the figure, 1, a semiconductor substrate; 2. a hafnium oxide layer; 3. a source electrode; 4. a drain electrode; 5. a perovskite thin film; 6. a gate electrode; 7. and passivating the protective layer.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
The invention provides a novel perovskite-based heterojunction photoelectric device, which comprises a semiconductor substrate 1 and a hafnium oxide layer 2 positioned on the upper surface of the semiconductor substrate, wherein a source electrode 3 and a drain electrode 4 are arranged on the upper surface of the hafnium oxide layer 2, a perovskite thin film 5 is arranged between the source electrode 3 and the drain electrode 4 on the upper surface of the hafnium oxide layer 2, and a gate electrode 6 is arranged on the lower surface of the semiconductor substrate 1, as shown in an embodiment I shown in figure 1.
In another embodiment of the present invention, as shown in fig. 2, a passivation layer 7 is disposed on the top surface of the perovskite thin film 5, and the passivation layer 7 may be SiO2，Al2O3，HfO2AlN, etc., may function to protect the perovskite thin film 5.
The thickness of the hafnium oxide layer 2 is 5-50nm, the thickness of the first embodiment and the second embodiment of the invention is about 20nm, under the condition of the thickness, the photoelectric performance of the device is greatly improved, R and EQE can reach 45A/W and 12445, and the thickness is excellent in a perovskite device.
The photoelectric device of the invention can be used as a phototriode or a photoelectric cell.
The perovskite film 5 is CsPbBr3Or CH3NH3PbI3And perovskite thin films like them. The perovskite thin film can be obtained by a spin coating method or an epitaxial growth method.
The source electrode 3 can be one of a Ti/Au combined electrode, a Ti/Al/Ni/Au combined electrode and a Ti/Al/Pt/Au combined electrode, and the drain electrode 4 can be one of a Ti/Au combined electrode, a Ti/Al/Ni/Au combined electrode and a Ti/Al/Pt/Au combined electrode.
A preparation method of a novel perovskite-based heterojunction photoelectric device comprises the following steps:
(1) at a distance of 1X 1cm2Using highly doped p-type Si as a substrate, ultrasonically cleaning the substrate in acetone for 10 minutes, and then alternately cleaning the substrate for 3 times by using ethanol and deionized water to obtain the high-conductivity semiconductorA bulk substrate 1;
(2) growing a layer of HfO on the surface of the semiconductor substrate 1 with high conductivity by the method of Atomic Layer Deposition (ALD)2A layer having a thickness of about 20 nm;
(3) designing the pattern of the source electrode 3 and the drain electrode 4 and the length of the channel through a mask, and evaporating on HfO in an electron beam evaporation mode2Depositing a source electrode 3 and a drain electrode 4 of Ti/Au material on the layer;
(4) by CsAc solution and PbBr2The solution is mixed according to the molar ratio of 1:4, and the reaction is immediately carried out to generate perovskite CsPbBr3Nanosheet, completing the reaction within 2 minutes, and preparing CsPbBr by dissolving toluene3A colloid;
(5) perovskite CsPbBr3The colloid was accurately dropped with a 1mm needle to HfO between the source electrode 3 and the drain electrode 42On the layer, placing on a heating table, drying at 110 ℃ for 5 minutes to obtain continuous CsPbBr after toluene in the colloid is completely removed3Film formation of CsPbBr3/HfO2A heterostructure photovoltaic device;
(6) in CsPbBr3And depositing a passivation protective layer 7 on the upper surface of the film.
When the photoelectric device is in use, the perovskite CsPbBr is added3The thin film region is set as an illumination region, and can be used for light detection or as a photocell.
The perovskite-based heterojunction photoelectric device prepared in the first embodiment of the invention is subjected to performance test, and the circuit connection is shown in figure 3, VgsRepresents the voltage between the gate electrode 6 and the source electrode 3, VdsRepresenting the voltage between the drain electrode 4 and the source electrode 3, the results were analyzed as follows:
the photovoltaic device as shown in FIG. 4a is at VgsDark current and photocurrent at 0V, and the photovoltaic device shown in figure 4b at VdsDark current and photocurrent contrast plots at 0V, as can be seen from the two plots: when V isgsWhen equal to 0V, at VdsA more obvious photocurrent can be obtained under the condition of less than 0; when V isdsWhen equal to 0V, at VgsA more pronounced photocurrent can be obtained at values greater than 0. The maximum ratio of the current magnitude under the illumination condition to the current magnitude under the dark environment can reach about 1000.
The photoelectric device shown in fig. 5 has different photocurrent magnitudes under different illumination powers at a wavelength of 450nm, and it can be seen from the graph that different illumination intensities can affect the magnitude of the photocurrent of the device under a fixed voltage. The current is increased under the condition that the illumination intensity is increased, and the current is reduced when the illumination intensity is reduced; and the device has good repeatability and stability.
The change curves of detectivity (D), responsivity (R) and External Quantum Efficiency (EQE) of the optoelectronic device under different optical powers are shown in FIG. 6, from which it can be seen that both D and R, EQE increase with the decrease of the illumination intensity, and at the illumination intensity of 0.15 μ W/cm2A maximum value is obtained. In particular, R and EQE can reach 45A/W and 12445, and the perovskite device is excellent.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The novel perovskite-based heterojunction photoelectric device is characterized by comprising a semiconductor substrate and a hafnium oxide layer positioned on the upper surface of the semiconductor substrate, wherein a source electrode and a drain electrode are arranged on the upper surface of the hafnium oxide layer, a perovskite thin film is arranged between the source electrode and the drain electrode on the upper surface of the hafnium oxide layer, and a grid electrode is arranged on the lower surface of the semiconductor substrate.
2. The perovskite-based novel heterojunction optoelectronic device of claim 1, wherein the upper surface of the perovskite thin film is provided with a passivation protective layer.
3. A novel perovskite-based heterojunction optoelectronic device according to claim 1, wherein the thickness of the hafnium oxide layer is 5-50 nm.
4. A novel perovskite-based heterojunction optoelectronic device according to claim 1, wherein the perovskite thin film is an organic perovskite material or an inorganic perovskite material.
5. A novel perovskite-based heterojunction optoelectronic device according to claim 1, wherein the perovskite thin film is obtained by a spin coating method or an epitaxial growth method.
6. A preparation method of a novel perovskite-based heterojunction photoelectric device is characterized by comprising the following steps:
(1) growing a hafnium oxide layer on the surface of the semiconductor substrate by an atomic layer deposition method;
(2) designing the pattern of a source electrode and a drain electrode and the length of a channel through a mask, and depositing the source electrode and the drain electrode on the hafnium oxide layer in an electron beam evaporation mode;
(3) preparing a perovskite thin film on the hafnium oxide layer between the source electrode and the drain electrode by a spin coating method or an epitaxial growth method to form perovskite/HfO2A heterostructure photovoltaic device.
7. The method for preparing a perovskite-based novel heterojunction photoelectric device as claimed in claim 6, wherein after obtaining the perovskite thin film, a passivation protection layer is deposited on the upper surface of the perovskite thin film.
8. The method for preparing a perovskite-based novel heterojunction photoelectric device according to claim 6, wherein the spin coating method is specifically as follows: firstly, preparing perovskite colloid by a chemical synthesis method; and dripping the perovskite colloid on the surface of the hafnium oxide layer between the source electrode and the drain electrode, and drying to obtain the continuous perovskite thin film.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114664961A (en) * | 2022-03-24 | 2022-06-24 | 湘潭大学 | Optical synapse device for simulating synapse plasticity in neural network and preparation method thereof |
| CN114784050A (en) * | 2022-06-17 | 2022-07-22 | 湖南大学 | Neuromorphic vision sensor and application and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114664961A (en) * | 2022-03-24 | 2022-06-24 | 湘潭大学 | Optical synapse device for simulating synapse plasticity in neural network and preparation method thereof |
| CN114784050A (en) * | 2022-06-17 | 2022-07-22 | 湖南大学 | Neuromorphic vision sensor and application and preparation method thereof |
| CN114784050B (en) * | 2022-06-17 | 2022-09-27 | 湖南大学 | Neuromorphic vision sensor and application and preparation method thereof |
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