CN111162181A - Hafnium-doped zinc oxide photoelectric detector and preparation method thereof - Google Patents
Hafnium-doped zinc oxide photoelectric detector and preparation method thereof Download PDFInfo
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- CN111162181A CN111162181A CN201911404847.5A CN201911404847A CN111162181A CN 111162181 A CN111162181 A CN 111162181A CN 201911404847 A CN201911404847 A CN 201911404847A CN 111162181 A CN111162181 A CN 111162181A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 7
- 238000000137 annealing Methods 0.000 claims abstract description 5
- 239000013077 target material Substances 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000004544 sputter deposition Methods 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 230000005525 hole transport Effects 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 4
- 230000031700 light absorption Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 238000000231 atomic layer deposition Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000001514 detection method Methods 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 238000000701 chemical imaging Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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Abstract
The invention relates to a hafnium-doped zinc oxide photoelectric detector and a preparation method thereof, wherein the structure of the device is FTO/Hf-ZnO/CH3NH3PbI3/spiro-OMe TAD/Au, and the device shows 8.95% of photoelectric conversion efficiency. Meanwhile, the device shows better photoelectric response performance, and the value of the device is as high as 7.0A/W under the bias voltage of 0; the device of vacuum annealing has the highest detection degree, and achieves the response degree of 1002. The invention has simple operation steps and low experimental cost, and the manufactured detector has higher responsivity and detection sensitivity.
Description
Technical Field
The invention relates to the technical field of semiconductor nano materials and photoelectric detectors, in particular to a hafnium-doped zinc oxide photoelectric detector and a preparation method thereof.
Background
The photoelectric detector has the advantages of wide raw material source, simple preparation, adjustable detection range and the like, and has great potential in the fields of image sensing, environmental monitoring, chemical and biological imaging and the like. Organic and inorganic hybrid lead-perovskite halide materials attract wide attention in recent years, have larger absorption coefficient, long carrier life and diffusion length, and thus have more applications in solar cells, LEDs, photodetectors and lasers. However, the poor stability makes the organic-inorganic hybrid lead-perovskite halide easily decomposed under the influence of water and oxygen molecules in the air, and limits the development of the organic-inorganic hybrid lead-perovskite halide in photoelectric devices. As a direct wide-band-gap semiconductor, ZnO has excellent photoelectric properties due to the forbidden band width of 3.3eV, is low in cost, mature in preparation process, and is a hotspot of current research. The performance of the device is improved by introducing doping into the oxide thin film, but no report of a hafnium-doped zinc oxide photodetector is found at present.
Disclosure of Invention
The invention aims to solve the technical problem of developing a hafnium-doped zinc oxide photoelectric detector and a preparation method thereof. In order to achieve the purpose, the invention provides the following technical scheme:
a hafnium-doped zinc oxide photoelectric detector mainly comprises transparent conductive glass, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a metal electrode, wherein the electron transport layer is formed by doping hafnium (Hf) into zinc oxide (ZnO) and is also a hole barrier layer, the perovskite light absorption layer is formed by CH3NH3PbI3 (perovskite) synthesized by a two-step method, the hole transport layer is formed by Spiro-OMe TAD and is also an electron barrier layer, and the metal electrode is formed by an Au film.
The specific preparation process and technology of the invention are as follows:
(1) respectively using deionized water, acetone and alcohol to perform ultrasonic transparent conductive glass FTO for 10 minutes, and then using an ultraviolet ozone environment to perform treatment for 20 minutes;
(2) the doped ZnO layer is prepared by spin coating: dissolving 1.0M zinc acetate solution in methanol solution, stirring for 15 min, and spin-coating on FTO at 3000r/min for 30 s; drying at 120 deg.C for 8min, and transferring to a muffle furnace for annealing for 1.5 h;
(3) the synthetic method of the perovskite layer adopts a traditional two-step method: firstly, 0.5M PbI is added2Dissolving in DMF (N, N-dimethylformamide), keeping the temperature at 60 ℃ for 10h to fully dissolve, and then filtering for later use; will CH3NH3Dissolving the I in isopropanol solution, and stirring for ten minutes for later use; PbI2The solution was spin coated onto the ZnO sample at 2000 rev for 30 seconds and then baked on a hot plate for 10 minutes, after which it was in CH3NH3I, soaking in an isopropanol solution for 3 minutes, and then drying;
(4) after the perovskite layer was formed on the sample, an HTM layer (hole transport layer) was spin-coated: spin-coating on the perovskite layer by using a spin-OMe TAD at 2000 revolutions for 30 seconds;
(5) the final gold electrode is evaporated at a rate of 50-60 nm.
A complete photoelectric detector can be manufactured, and meanwhile, the photoelectric conversion efficiency is higher.
Specifically, the preparation of the doped ZnO is carried out by utilizing a magnetron sputtering technology or an atomic layer deposition method, a ZnO target material is placed on a target platform, a doped target material Hf target material is placed on the target platform, different power ratios are selected for the Hf target material and the ZnO target material for simultaneous sputtering, materials with doping content of 6% -10% are prepared by utilizing sputtering power with different ratios, the magnetron sputtering vacuum degree is less than 10Pa, the substrate temperature is room temperature, the working pressure is 0.3-0.8 Pa, the sputtering power of the Hf target material is 10-30W, and the sputtering power of the ZnO target material is 50-80W.
The device structure is FTO/Hf-ZnO/CH3NH3PbI3/spiro-OMe TAD/Au, and the device shows the photoelectric conversion efficiency of 8.95%. Meanwhile, the device shows better photoelectric response performance, and the value of the device is as high as 7.0A/W under the bias voltage of 0; the device of vacuum annealing has the highest detection degree, and achieves the response degree of 1002.
The advantages and the characteristics of the invention are as follows:
(1) the photoelectric detector manufactured by the invention has the advantages of simple manufacturing process, low cost of experimental raw materials and environmental friendliness, and the unique structure provides a new way for the development of manufacturing high-performance detectors.
(2) The invention has the double performance of cell conversion efficiency and photoelectric detection, and shows the photoelectric conversion efficiency of 8.95 percent and the responsivity of 7.0A/W under 0 bias voltage.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Respectively using deionized water, acetone and alcohol to perform ultrasonic transparent conductive glass FTO for 10 minutes, and then using an ultraviolet ozone environment to perform treatment for 20 minutes.
(2) The doped ZnO layer is prepared by spin coating. The solution was dissolved in 1.0M zinc acetate solution in methanol and stirred for 15 minutes and spun onto FTO at 3000r/min for 30 seconds. Drying at 120 deg.C for 8min, and transferring to muffle furnace for annealing for 1.5 h. The preparation of the doped ZnO is carried out by utilizing a magnetron sputtering technology or an atomic layer deposition method, and the doped ZnO is placed on a target platform as a ZnO target material, meanwhile, a doped target material Hf target material is placed on the target platform, sputtering is carried out on the Hf target material and the ZnO target material according to different power ratios, materials with doping content of 6% -10% are prepared by utilizing sputtering power with different ratios, the magnetron sputtering vacuum degree is less than 10Pa, the substrate temperature is room temperature, the working pressure is 0.3-0.8 Pa, the sputtering power of the Hf target material is 10-30W, and the sputtering power of the ZnO target material is 50-80W.
(3) The perovskite layer synthesis method employs a conventional two-step process. 0.5M PbI2 was dissolved in DMF (N, N-dimethylformamide), incubated at 60 ℃ for 10 hours to dissolve it sufficiently, and then filtered for future use. CH3NH3I was dissolved in the isopropanol solution and stirred for ten minutes until use. The PbI2 solution was spin-coated on the ZnO sample at 2000 rpm for 30 seconds, then baked dry on a hot bench, 10 minutes later, immersed in CH3NH3I isopropanol solution for 3 minutes, and then blown dry.
(4) After the perovskite layer was formed on the sample, an HTM layer (hole transport layer) was spin-coated. Here, a spin-OMe TAD was used to spin coat the perovskite layer at 2000 revolutions for 30 seconds.
(5) The final gold electrode is evaporated at a rate of 50-60 nm.
A complete photoelectric detector can be manufactured, and meanwhile, the photoelectric conversion efficiency is higher.
Claims (3)
1. A hafnium-doped zinc oxide photodetector, comprising: mainly comprises transparent conductive glass, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a metal electrode, wherein the electron transport layer is formed by doping hafnium (Hf) element into zinc oxide (ZnO) and is also a hole blocking layer(ii) a The perovskite light absorption layer is CH synthesized by a two-step method3NH3PbI3(perovskite) formation; the hole transport layer is composed of a Spiro-OMe TAD and is also an electron blocking layer; the metal electrode is composed of an Au film.
2. The photodetector of claim 1, wherein: the specific preparation process comprises the following steps:
(1) respectively using deionized water, acetone and alcohol to perform ultrasonic transparent conductive glass FTO for 10 minutes, and then using an ultraviolet ozone environment to perform treatment for 20 minutes;
(2) the doped ZnO layer is prepared by spin coating: dissolving 1.0M zinc acetate solution in methanol solution, stirring for 15 min, and spin-coating on FTO at 3000r/min for 30 s; drying at 120 deg.C for 8min, and transferring to a muffle furnace for annealing for 1.5 h;
(3) the synthetic method of the perovskite layer adopts a traditional two-step method: firstly, 0.5M PbI is added2Dissolving in DMF (N, N-dimethylformamide), keeping the temperature at 60 ℃ for 10h to fully dissolve, and then filtering for later use; will CH3NH3Dissolving the I in isopropanol solution, and stirring for ten minutes for later use; PbI2The solution was spin coated onto the ZnO sample at 2000 rev for 30 seconds and then baked on a hot plate for 10 minutes, after which it was in CH3NH3I, soaking in an isopropanol solution for 3 minutes, and then drying;
(4) after the perovskite layer was formed on the sample, an HTM layer (hole transport layer) was spin-coated: spin-coating on the perovskite layer by using a spin-OMe TAD at 2000 revolutions for 30 seconds;
(5) the final gold electrode is evaporated at a rate of 50-60 nm.
3. The photodetector of claim 2, wherein: the preparation of the doped ZnO is realized by utilizing a magnetron sputtering technology or an atomic layer deposition method, a ZnO target material is placed on a target platform, a doped target material Hf target material is placed on the target platform, different power ratios are selected for the Hf target material and the ZnO target material for simultaneous sputtering, materials with doping content of 6% -10% are prepared by utilizing sputtering power with different ratios, the magnetron sputtering vacuum degree is less than 10Pa, the substrate temperature is room temperature, the working pressure is 0.3-0.8 Pa, the sputtering power of the Hf target material is 10-30W, and the sputtering power of the ZnO target material is 50-80W.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU202307U1 (en) * | 2020-10-21 | 2021-02-11 | Виктор Юрьевич Тимошенко | PHOTOELECTRIC CONVERTER |
| CN115821317A (en) * | 2022-11-22 | 2023-03-21 | 四川大学 | Method for improving photoelectric catalytic performance of iron oxide nanorod |
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Application publication date: 20200515 |