CN102222771A - Organic and inorganic hybridized semiconductor ultraviolet photovoltaic detector - Google Patents
Organic and inorganic hybridized semiconductor ultraviolet photovoltaic detector Download PDFInfo
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- CN102222771A CN102222771A CN2011101801094A CN201110180109A CN102222771A CN 102222771 A CN102222771 A CN 102222771A CN 2011101801094 A CN2011101801094 A CN 2011101801094A CN 201110180109 A CN201110180109 A CN 201110180109A CN 102222771 A CN102222771 A CN 102222771A
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Abstract
The invention discloses an organic and inorganic hybridized semiconductor ultraviolet photovoltaic detector, belonging to the technical field of photoelectrons, in particular a semiconductor ultraviolet photovoltaic detector technology. The organic and inorganic hybridized semiconductor ultraviolet photovoltaic detector disclosed by the invention comprises a substrate, a negative electrode layer, a positive electrode layer and an ultraviolet semiconductor material layer, and is characterized in that: the ultraviolet semiconductor material layer of the detector is formed by hybridizing an organic ultraviolet semiconductor and an inorganic ultraviolet semiconductor, wherein in the ultraviolet semiconductor, a ZnO nano-rods array is used as an n-type inorganic semiconductor, and a wide-band-gap organic ultraviolet semiconductor is used as a p-type organic semiconductor to form a pn junction. The detector disclosed by the invention has the characteristics of large planar array, fast response speed and low power consumption.
Description
Technical field
The invention belongs to the photoelectron technology field, especially a kind of semiconductor ultraviolet photovoltaic detector technology.
Background technology
Therefore advantages such as ultraviolet detector has can be at working and room temperature, need not freeze, detectivity height, preparation cost is low, false alarm rate is low are approached the army and the people field such as alarm and are had a wide range of applications at environmental monitoring, forest fire protection, astrosurveillance, scientific research, guided missile.
The ultraviolet semiconductor detector is divided into guide type ultraviolet semiconductor detector and photovoltaic type ultraviolet semiconductor detector, generally speaking photoconductive detectors preparation technology is simple, preparation cost is low, but shortcoming is response time length, is difficult for realization face battle array, device work power consumption height.The photovoltaic type ultraviolet detector have the response time short, low in energy consumption, be easy to characteristics such as realization face battle array, so the photovoltaic type ultraviolet detector is an emphasis of ultraviolet detector research and development.
At present, the material that is used to prepare ultraviolet detector mainly contains material systems such as GaN, ZnO and Si.Because the Si base ultraviolet detector needs the high filter plate of cost, therefore limited the application of Si base ultraviolet detector.The GaN material then because of its preparation temperature height, and Mg doped p type GaN be difficult for to obtain, and hindered the development of GaN base ultraviolet detector.Wide band gap semiconducter ZnO is owing to have the band gap of broad, and be widely used in the ultraviolet photoelectron preparation of devices, yet because the existence of self compensation effect, the acquisition of p type ZnO material at present remains a technical barrier, has limited the application of ZnO in the ultraviolet light photo device.
Existing most organic semiconducting materials all is a p N-type semiconductor N material.If inorganic ZnO material of n type and p type organic ultraviolet semi-conducting material are combined, form organic and inorganic semiconductor pn heterojunction, the heterojunction of these novel structures had both combined organic semi-conductor large tracts of land and flexible advantage, have the advantage of inorganic semiconductor high mobility again concurrently, therefore can design and make how novel opto-electronic device, their performance is that independent inorganic semiconductor heterojunction or organic semiconductor heterojunction are not available.
The derivative of fluorenes is widely used on the functional materials such as light-emitting diode, field-effect transistor, electric charge transfering reagent and nonlinear optical material, yet in the research in organic optoelectronic field but seldom about fluorenes, discover that fluorenes has very strong UV absorption at the ultraviolet non-solar-blind band, at ultraviolet band stronger luminescence generated by light is arranged also, therefore the more deep application that can in the ultraviolet detector technology, get.
Summary of the invention
The ZnO of being exactly inorganic semiconductor material to be solved by this invention is not easy to realize the doping of p type, is difficult for forming the pn knot, to realize the problem of photovoltaic type ultraviolet semiconductor detector, provides a kind of organic and inorganic hybridization semiconductor ultraviolet photovoltaic detector.
A kind of organic and inorganic hybridization semiconductor ultraviolet photovoltaic detector of the present invention, comprise substrate, negative electrode layer, anode electrode layer and ultraviolet semiconductor material layer, the ultraviolet semiconductor that it is characterized in that this detector is formed by organic ultraviolet semiconductor and inorganic ultraviolet semiconductor hybrid, with the ZnO nanometer stick array is n type inorganic semiconductor, is that p type organic semiconductor forms the pn knot with broad-band gap organic ultraviolet semiconductor.
Described broad-band gap organic ultraviolet semi-conducting material is fluorenes, anthracene, hexachlorobenzene, poly-fluorenes or PBD.
Needing growth one layer thickness before the described ZnO nanometer stick array growth is the ZnO inculating crystal layer of 10～100nm, is used for the induced growth of follow-up ZnO nanometer stick array, so that form structurally ordered ZnO nanometer stick array.
Described n type inorganic semiconductor is perpendicular to the ZnO nanometer stick array of substrate, and its length is 500～1500nm, and diameter is 60～85nm, to increase the efficiency of transmission of light induced electron.
Fill the PMMA polymer of electric insulation in the described ZnO nanometer stick array, its thickness is 470～1470nm, the ZnO nanometer rods is exposed filler 30～50nm of PMMA, so that follow-up p molded breadth band gap organic ultraviolet semiconductor contacts with the inorganic ultraviolet semiconductor maximization of n type ZnO, prevent the cross-talk of device, increase the stability of device.
Described p molded breadth band gap organic ultraviolet semi-conducting material forms in top thermal evaporation of ZnO nanometer stick array or spin coating, and its thickness is 80～150nm.
Deposit the molybdenum oxide film of 5～30nm thickness on the described p molded breadth band gap organic ultraviolet semiconductor.
Described anode electrode layer is thermal evaporation or translucent high work function metal Au of electron beam deposition or the formation of Pt film on the molybdenum oxide film, is used to collect photohole.
Described detector negative electrode layer is an ito thin film, and thickness is 100～300nm.
ITO clear bottom electrode is a negative pole during work, collects light induced electron, and semi-transparent metals Au or Pt are anodal, collect photohole, and the ZnO nanometer stick array has good electronical line shaft to transport capability, makes detector of the present invention have good performance.
Detector of the present invention has following advantage:
Big face battle array, ZnO nanometer rods of the present invention, organic semiconductor thin-film etc. are all realized large-area preparation easily, therefore can realize big face battle array, high density detecting element array based on the detector of this technology.
Response speed is fast, and organic and inorganic hybridization semiconductor ultraviolet detector of the present invention are the photovoltaic type device, light induced electron and hole dissociating, transporting and the collection efficiency height under internal electric field, and it is short to transport distance, so the response speed of detector is fast.
Low-power consumption, detector of the present invention are the photovoltaic type ultraviolet detector, can work under zero offset or low-voltage bias condition, so device power consumption are low.
Description of drawings
Fig. 1 is embodiment 1 a panel detector structure schematic diagram.
Fig. 2 is among the embodiment 14 * 10
-3The cyclohexane solution UV-Vis abosrption spectrogram of M fluorenes.
Fig. 3 is the luminescence generated by light spectrogram of embodiment 1 fluorenes solution under the 300nm excitation wavelength.
Fig. 4 be embodiment 1 detector unglazed according to the time the I-V curve chart.
Fig. 5 is the ultraviolet light response curve chart of embodiment 1 detector.
Wherein, substrate 1, negative electrode layer 2, inculating crystal layer 3, nanometer stick array 4, PMMA 5, and the broad-band gap organic ultraviolet partly leads 6, molybdenum oxide film 7, anode electrode layer 8.
Embodiment
Embodiment 1: a kind of organic and inorganic hybridization semiconductor ultraviolet photovoltaic detector of the present invention forms following layer of structure from substrate successively to the anode electrode layer:
(1) quartz plate or sheet glass substrate 1;
(2) the negative electrode layer 2 of the transparent ito thin film formation that 150nm is thick;
(3) the ZnO inculating crystal layer 3 that 50nm is thick;
(4) 1000nm is long, and diameter is the ZnO nanometer stick array 4 of 60nm;
(5) be filled in PMMA5 in the ZnO nanometer stick array;
(6) the p molded breadth band gap organic ultraviolet semiconductor 6 that 85nm is thick, its material is a fluorenes, wherein 30nm is thick is embedded in the ZnO nanometer stick array 4, thick ZnO nanometer stick array 4 outsides that are exposed to of 55nm;
(7) the molybdenum oxide film 7 that 20nm is thick;
(8) high work function metal Au or Pt film anode electrode layer 8.
This detector is to get by following processing step preparation:
(1) cleaning base plate 1 quartz plate or sheet glass, oven dry;
(2) on quartz or glass substrate 1, prepare the transparency electrode ito thin film of 150nm with magnetron sputtering or sol-gel technique, as the negative electrode layer 2 of photovoltaic detector;
(3) on ito thin film, prepare the thick ZnO inculating crystal layer 3 of 50nm with magnetron sputtering technique, sol-gel technique or PLD technology;
(4) preparing length with hydrothermal technique on ZnO inculating crystal layer 3 is 1000nm, and diameter is the ZnO nanometer stick array 4 of 60nm;
(5) under 1000 rev/mins of rotating speeds, in ZnO nanometer stick array 4, fill PMMA5 with photoresist spinner,, allow ZnO nanometer stick array 4 30nm that appears in 80 ℃ of oven dry;
(6) deposit the thick p molded breadth band gap organic ultraviolet semiconductor 6 of 85nm with thermal evaporation techniques on ZnO nanometer stick array 4, its material is a fluorenes, and wherein 30nm is thick is embedded in the ZnO nanometer stick array 4, thick ZnO nanometer stick array 4 outsides that are exposed to of 55nm;
(7) then on p type organic ultraviolet semiconductor fluorenes, prepare the thick molybdenum oxide film 7 of 20nm, to increase the collection efficiency of photohole with thermal evaporation techniques;
(8) last, high work function metal Au of thermal evaporation or electron beam deposition or Pt film on molybdenum oxide film 7 are as the anode electrode layer 8 of detector.
Embodiment 2: a kind of organic and inorganic hybridization semiconductor ultraviolet photovoltaic detector of the present invention forms following layer of structure from substrate successively to the anode electrode layer:
(1) quartz plate or sheet glass substrate 1;
(2) the negative electrode layer 2 of the transparent ito thin film formation that 120-250nm is thick;
(3) the ZnO inculating crystal layer 3 that 20-60nm is thick;
(4) 600-1200nm is long, and diameter is the ZnO nanometer stick array 4 of 70-80nm;
(5) be filled in PMMA5 in the ZnO nanometer stick array 4, ZnO nanometer stick array 4 35-40nm that appears;
(6) the thick p molded breadth band gap organic ultraviolet semiconductor 6 of preparation 90-120nm, its material are anthracene, hexachlorobenzene, poly-fluorenes or PBD film, and wherein a part is embedded in the ZnO nanometer stick array 4, and remainder is exposed to ZnO nanometer stick array 4 outsides;
(7) the thick molybdenum oxide film 7 of preparation 20-30nm;
(8) high work function metal Au or Pt film anode electrode layer 8.
This detector is to get by following processing step preparation:
(1) cleaning base plate 1 quartz plate or sheet glass, oven dry;
(2) the transparency electrode ito thin film of preparation 120-250nm on quartz or glass substrate 1 is as the negative electrode layer 2 of photovoltaic detector;
(3) the thick ZnO inculating crystal layer 3 of preparation 20-60nm on ITO;
(4) preparing length with hydrothermal technique on ZnO inculating crystal layer 3 is 600-1200nm, and diameter is the ZnO nanometer stick array 4 of 70-80nm;
(5) under 800-1500 rev/min of rotating speed, in ZnO nanometer stick array 4, fill PMMA5 with photoresist spinner,, allow ZnO nanometer stick array 4 35-40nm that appears in 80 ℃ of oven dry;
(6) the thick p molded breadth band gap organic ultraviolet semiconductor 6 of deposition 90-120nm on ZnO nanometer stick array 4, its material is anthracene or hexachlorobenzene, poly-fluorenes or PBD, wherein a part is embedded in the ZnO nanometer stick array 4, remainder is exposed to ZnO nanometer stick array 4 outsides, to guarantee the ZnO nanometer rods 35-40nm that appears;
(7) the thick molybdenum oxide film 7 of preparation 20-30nm on p molded breadth band gap organic ultraviolet semiconductor 6 is to increase the collection efficiency of photohole;
(8) last, high work function metal Au of preparation or Pt film on molybdenum oxide film 7 are as the anode electrode layer 8 of detector.
Claims (9)
1. organic and inorganic hybridization semiconductor ultraviolet photovoltaic detector, comprise substrate (1), negative electrode layer (2), anode electrode layer (8) and ultraviolet semiconductor material layer, the ultraviolet semiconductor that it is characterized in that this detector is formed by organic ultraviolet semiconductor and inorganic ultraviolet semiconductor hybrid, with ZnO nanometer stick array (4) is n type inorganic semiconductor, is that p type organic semiconductor forms the pn knot with broad-band gap organic ultraviolet semiconductor (6).
2. a kind of organic and inorganic hybridization semiconductor ultraviolet photovoltaic detector as claimed in claim 1 is characterized in that described broad-band gap organic ultraviolet semi-conducting material is fluorenes, anthracene, hexachlorobenzene, poly-fluorenes or PBD.
3. a kind of organic and inorganic hybridization semiconductor ultraviolet photovoltaic detector as claimed in claim 1 is characterized in that before described ZnO nanometer stick array (4) growth need growth one layer thickness be the ZnO inculating crystal layer (3) of 10～100nm.
4. a kind of organic and inorganic hybridization semiconductor ultraviolet photovoltaic detector as claimed in claim 1, it is characterized in that described n type inorganic semiconductor is perpendicular to the ZnO nanometer stick array (4) of substrate (1), its length is 500～1500nm, and diameter is 60～85nm.
5. a kind of organic and inorganic hybridization semiconductor ultraviolet photovoltaic detector as claimed in claim 1, it is characterized in that filling in the described ZnO nanometer stick array (4) the polymer P MMA(5 of electric insulation), its thickness is 470～1470nm, and the ZnO nanometer rods is exposed PMMA(5) filler 30～50nm.
6. a kind of organic and inorganic hybridization semiconductor ultraviolet photovoltaic detector as claimed in claim 1, it is characterized in that described p molded breadth band gap organic ultraviolet semiconductor (6) forms in ZnO nanometer stick array (4) top thermal evaporation or spin coating, its thickness is 80～150nm.
7. a kind of organic and inorganic hybridization semiconductor ultraviolet photovoltaic detector as claimed in claim 1 is characterized in that depositing on the described p molded breadth band gap organic ultraviolet semiconductor (6) the molybdenum oxide film (7) of 5～30nm thickness.
8. a kind of organic and inorganic hybridization semiconductor ultraviolet photovoltaic detector as claimed in claim 1 is characterized in that described anode electrode layer (8) is in upward thermal evaporation or translucent high work function metal Au of electron beam deposition or the formation of Pt film of molybdenum oxide film (7).
9. a kind of organic and inorganic hybridization semiconductor ultraviolet photovoltaic detector as claimed in claim 1 is characterized in that described detector negative electrode layer (2) is an ito thin film, and thickness is 100～300nm.
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Cited By (11)
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| CN103311439A (en) * | 2013-05-17 | 2013-09-18 | 中国科学院化学研究所 | Thin film photoconductive detector and manufacturing method and application thereof |
| CN103441216A (en) * | 2013-08-29 | 2013-12-11 | 吉林大学 | Ultraviolet light detector based on titanium dioxide nanometer bowl array and manufacturing method thereof |
| CN103594631A (en) * | 2013-06-25 | 2014-02-19 | 北京科技大学 | Novel self-driven ultraviolet detector and manufacturing method thereof |
| CN105390565A (en) * | 2015-11-06 | 2016-03-09 | 昆明物理研究所 | Solution-technology-based ZnO and PFO micro-nano heterojunction ultraviolet photovoltaic detector |
| CN105390615A (en) * | 2015-11-30 | 2016-03-09 | 中国科学技术大学 | UV light sensor |
| CN105428534A (en) * | 2015-11-06 | 2016-03-23 | 昆明物理研究所 | Ultraviolet photovoltaic detector with ZnO nanorod and phenanthrene nano heterogeneous composite structure |
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| CN108735833A (en) * | 2018-05-30 | 2018-11-02 | 张权岳 | A kind of flexible wide spectrum photodetector of organic/inorganic pn-junction nano-array and preparation method thereof |
| CN109244244A (en) * | 2018-09-10 | 2019-01-18 | 电子科技大学中山学院 | Ordered heterojunction photovoltaic device and preparation method thereof |
| CN111799380A (en) * | 2020-07-21 | 2020-10-20 | 湘南学院 | Organic-inorganic composite photoconductive detector and preparation method and application thereof |
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2011
- 2011-06-30 CN CN2011101801094A patent/CN102222771A/en active Pending
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Cited By (17)
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| CN103311439B (en) * | 2013-05-17 | 2015-07-15 | 中国科学院化学研究所 | Thin film photoconductive detector and manufacturing method and application thereof |
| CN103311439A (en) * | 2013-05-17 | 2013-09-18 | 中国科学院化学研究所 | Thin film photoconductive detector and manufacturing method and application thereof |
| CN103594631A (en) * | 2013-06-25 | 2014-02-19 | 北京科技大学 | Novel self-driven ultraviolet detector and manufacturing method thereof |
| CN103441216B (en) * | 2013-08-29 | 2016-03-23 | 吉林大学 | A kind of based on TiO 2ultraviolet light detector of nano bowl array and preparation method thereof |
| CN103441216A (en) * | 2013-08-29 | 2013-12-11 | 吉林大学 | Ultraviolet light detector based on titanium dioxide nanometer bowl array and manufacturing method thereof |
| RU2586263C1 (en) * | 2014-12-08 | 2016-06-10 | Общество с ограниченной ответственностью "Аналитические приборы и специальные технологии защиты" | Hybrid multilayer photoelectric converter |
| CN106153223A (en) * | 2015-03-27 | 2016-11-23 | 北京纳米能源与系统研究所 | Strain gauge array and preparation method thereof and stress distribution sensor-based system and method for sensing |
| CN105390565A (en) * | 2015-11-06 | 2016-03-09 | 昆明物理研究所 | Solution-technology-based ZnO and PFO micro-nano heterojunction ultraviolet photovoltaic detector |
| CN105428534A (en) * | 2015-11-06 | 2016-03-23 | 昆明物理研究所 | Ultraviolet photovoltaic detector with ZnO nanorod and phenanthrene nano heterogeneous composite structure |
| CN105428534B (en) * | 2015-11-06 | 2017-08-25 | 昆明物理研究所 | A kind of ultraviolet photovoltaic detector with ZnO nanorod with luxuriant and rich with fragrance nano heterogeneous composite construction |
| CN105390615A (en) * | 2015-11-30 | 2016-03-09 | 中国科学技术大学 | UV light sensor |
| CN105390615B (en) * | 2015-11-30 | 2018-10-23 | 中国科学技术大学 | A kind of ultraviolet light transducer |
| CN108735833A (en) * | 2018-05-30 | 2018-11-02 | 张权岳 | A kind of flexible wide spectrum photodetector of organic/inorganic pn-junction nano-array and preparation method thereof |
| CN109244244A (en) * | 2018-09-10 | 2019-01-18 | 电子科技大学中山学院 | Ordered heterojunction photovoltaic device and preparation method thereof |
| CN109244244B (en) * | 2018-09-10 | 2024-03-19 | 电子科技大学中山学院 | Ordered heterojunction photovoltaic device and preparation method thereof |
| CN111799380A (en) * | 2020-07-21 | 2020-10-20 | 湘南学院 | Organic-inorganic composite photoconductive detector and preparation method and application thereof |
| CN111799380B (en) * | 2020-07-21 | 2022-11-22 | 湘南学院 | Organic-inorganic composite photoconductive detector, and preparation method and application thereof |
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Application publication date: 20111019 |