CN101976729A - Plane-configured organic infrared or ultraviolet photovoltaic semiconductor detector - Google Patents
Plane-configured organic infrared or ultraviolet photovoltaic semiconductor detector Download PDFInfo
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Abstract
The invention relates to the technical field of photoelectron, in particular to a plane-configured organic infrared or ultraviolet photovoltaic semiconductor detector which comprises a substrate, an organic infrared or ultraviolet photovoltaic semiconductor, a low work function electrode and a high work function electrode. The detector is characterized in that the low work function electrode and the high work function plane are in the same plane. The plane-configured organic infrared or ultraviolet photovoltaic semiconductor detector technology of the invention can be applied to manufacture a plane-configured organic infrared photovoltaic semiconductor detector and a plane-configured organic ultraviolet photovoltaic semiconductor detector. Compared with the optical waveguide detector, the detector of the invention has the advantages of fast response speed, low power dissipation, easy formation of array, no need of offsetting and the like. In addition, the detector of the invention has the characteristics of low cost, easy realization of controllable electrical resistivity of large area photosensing materials, no need of refrigeration, realization of flexible processing and the like, thus having important potential application values in the military field, the civil field and some specific fields.
Description
Technical field
The present invention relates to the photoelectron technology field, especially photovoltaic type organic semiconductor detector.
Background technology
Organic infrared/ultraviolet semiconductor (Organic Infrared/Ultraviolet Semiconductor) is defined as next class material: electromagnetic infrared/ultraviolet band has organic molecule, organometallic complex, organic oligomer or the high polymer of photoelectricity or photovoltaic effect.The notable feature of this type of material is different from infrared/ultraviolet inorganic semiconductor is that intermolecular force is based on active forces such as van der waals force, hydrogen bond, π-pi-electron active force, coordinate bonds, therefore being different from intermolecular is main inorganic infrared/ultraviolet semi-conducting material by active forces such as covalent bond, ionic bonds, organic infrared/the ultraviolet semi-conducting material can prepare film on monocrystalline, polycrystalline, amorphous even flexible substrate.
Organic semiconducting materials is with respect to inorganic semiconductor material, have inexpensive light weight, dissolubility good, easily be processed into large area flexible device and cut out the advantage of regulation and control photoelectric properties by molecule.Organic semiconducting materials if can be realized infrared or ultraviolet detection as a kind of photoelectric response material, then can overcome many shortcomings of inorganic semiconductor material.Therefore western developed country has begun organic semiconducting materials application study in this respect in recent years.
Infrared technique is the important component part of modern optical electronic technology field, is a kind of new and high technology of generation, transmission, conversion, detection and the application of research infrared radiation.Military Application is the major impetus that promotes Development of Infrared Technique, all be absolutely necessary in modern war and future war tactics and strategic means such as infrared imaging, infrared guidance, infrared early warning.Infrared Detectors is one of most important applications in the infrared technique, and infrared detector material is the direct factor that influences performances of IR, and the development of infra-red material can directly influence the performance and the application of Infrared Detectors.
The ultraviolet detection technology is subjected to the military day by day and payes attention to as the important supplement of infrared detection technique, and one of its important Military Application is that guided missile approaches the ultraviolet alarm.
The quantum type Infrared Detectors of practicability mainly is that mercury cadmium telluride is main inorganic material at present, the problem that these materials exist is: preparation cost height, complex process, can not especially prepare on silicon substrate and metal electrode at cheap substrate, thereby limit the application of the Infrared Detectors with important Military Application.
The existing material that is used to make ultraviolet detector mainly contains inorganic wide bandgap semiconductor materials such as ZnO, GaN, SiC.Their popular feature is: the preparation temperature height, the application band narrow range costs an arm and a leg etc., thereby has limited the application of the ultraviolet detector with important Military Application.
The research of organic infrared detector material is then just carried out in recent years.General organic/polymeric material does not have photolytic activity at the region of ultra-red greater than 1.00 m wave-length coverages.End to 2003, pure organic materials also of no use is made greater than the infraluminescence of 1.00 m wavelength and the report of light detecting device.Have only Siemens and Oldenburg university to report visible light-ultraviolet detector at present based on organic semiconducting materials, though the researcher of other countries has synthesized the organic semiconducting materials with ultraviolet absorption characteristic, such as 2,6-is two to replace indenofluorene derivative and dithiocarbamate etc., but the report of rarely found organic UV detector aspect.
Because the problem that present organic infrared semiconductor material mainly exists is response wave band still not ideal enough (being up to 1.60um), the infrared response wave band also is lower than first infrared window, does not reach the requirement of practicability infrared detector material.So the research to longer infrared response band extension is the important research direction of organic from now on infrared semiconductor material for detector.By existing organic semiconducting materials being carried out modification its response wave band is further expanded, reach the practicability wave band.Organic infrared semiconductor material film can be non-single crystal thin film, if can develop this kind material and be applied to Infrared Detectors, not only can realize low cost, the device preparation of big face battle array, even can make the target of direct growth Infrared Detectors on reading circuit become possibility, fundamentally change the method for traditional " long material, make device ".From combination property, the silicon reading circuit is the signal processing circuit of infrared focal plane detector the best.After silicon reading circuit preparation was finished, its surface was amorphous and microcrystalline state, therefore, and the infrared detector material of growing single-crystal attitude in its surface.If be implemented in the target of " long device " on the reading circuit, directly the preparation infrared detector material is just possible on its surface to have only breakthrough, and organic infrared semiconductor material film can satisfy this requirement.
The application study of the organic semiconducting materials of external report at present mainly concentrates on Organic Light Emitting Diode, organic field effect tube and the organic photovoltaic solar cell.It is organic molecule, organic oligomer and the conjugated polymer polymer etc. of representative that organic semiconducting materials mainly contains with metallo-chelate and rare earth ion complex compound, and successfully is applied to every field such as information, the energy, environmental protection, medical treatment, agricultural, national defence.
Organic semiconducting materials if can be realized infrared or ultraviolet detection as a kind of photoelectric response material, then can overcome the shortcoming of above inorganic semiconductor material, thereby is expected to be prepared into the infrared or ultraviolet detector of low cost, big face battle array.
The device that the organic photovoltaic detector of vertical stratification is to use multi-functional layer material to constitute, the photovoltaic device of this structure is beneficial to the integrated of device, has but lost part light inevitably.
Summary of the invention
The objective of the invention is a kind of low cost, large tracts of land, technology simple plane structure organic ultraviolet or infrared semiconductor photovoltaic detector of being convenient to by the technology preparation of solution or thermal evaporation that will design the loss of light at the organic photovoltaic detector of vertical stratification.
The organic infrared photovoltaic semiconductor detector of a kind of plane configuration of the present invention comprises: substrate, organic infrared semiconductor, low work function electrode and high work function electrode is characterized in that: low work function electrode and high work function electrode are positioned at same plane.
A kind of plane configuration organic ultraviolet photovoltaic semiconductor detector comprises: substrate, organic ultraviolet semiconductor, low work function electrode and high work function electrode is characterized in that: low work function electrode and high work function electrode are positioned at same plane.
Said high work function electrode and low work function electrode are in same plane looping or interdigitation or spiral type or bar shaped or snakelike.
Said substrate comprises Si base substrate; Amorphous glass, quartz substrate; Polycrystalline ceramics substrate and flexible plastic substrate.
Said organic ultraviolet semiconductor layer comprises: anthracene, phenanthrene, fluorenes and be the derivative of parent with them or be polymer of monomers with they and they derivative;
Said organic infrared semiconductor comprises that phthalocyanine erbium, phthalocyanine gadolinium etc. are near infrared light has the phthalocyanine rare earth with sandwich structure, dithiol alkene platinum, the graphite of photoelectric respone rare, graphene oxide etc. has photoelectric respone to infrared light material.
Said organic infrared semiconductor or organic ultraviolet semi-conducting material comprise the organic semiconducting materials of donor doping or acceptor doping.
Said low work function electrode comprises Na, Ag, Mg, Al, Zn, Ti, Cd, Ca, K, Li, U, In, Cs, Gd, Hf, La, Mn, Nb, Pb, V, Zr electrode, and the single or multiple lift alloying metal electrode that is combined to form by them.
Said high work function electrode material comprises Au, Cu, Cr, Ni, Co, C, Si, Pd, Pt, Se, ITO, AZO, Fe, Ir, Os, and the composite material that is combined to form by them.
Said electrode can be used thermal evaporation, magnetron sputtering, pulsed laser deposition, the independent technology of electron beam evaporation or combination technique preparation.
Device preparation technology variation of the present invention, both can be earlier on substrate the electrode of two kinds of different work contents of preparation, preparation organic semiconductor light-sensitive material on electrode again; Can on substrate, prepare the organic photosensitive material earlier again, relend the electrode that helps mask plate and technique of counterpoint to prepare two kinds of different work contents respectively.Also promptly, the mode that forms device has two kinds, and a kind of is from bottom to top technology, another kind is top-down technology, wherein, structure from bottom to top is: on substrate, make the low work function electrode and the high work function electrode of certain figure earlier, and then preparation organic ultraviolet or infrared semiconductor; Top-down structure is: prepare organic ultraviolet or infrared semiconductor earlier on substrate, and then prepare the low work function electrode and the high work function electrode of certain figure.
Organic ultraviolet of the present invention or infra-red sensitive material can be by selecting the dissolution with solvents of certain polarity, certain viscosity, by solution casting, spin coating, lift, roller coating, printing, self assembly, mode prepare light-sensitive material, also can prepare the light-sensitive material film by the method for thermal evaporation.
Concrete electrode structure of the present invention comprises: electrode structures such as interdigitated, bar shaped, annulus, spirality.
The device that the organic photovoltaic detector of vertical stratification is to use multi-functional layer material to constitute, the photovoltaic device of this structure is beneficial to the integrated of device, has but lost part light inevitably.
Planar structure can consider that substrate is to surveying optical transmission, so the selection degree of freedom of material is very big; In addition since survey only shine directly into light-sensitive material, so planar structure also can be avoided absorption and the reflection to light of other functional layers or electrode material; Because the device preparation technology of planar structure is simple relatively, thus be easy to realize large-scale batch process, thus can effectively reduce device cost; The light-sensitive material film of plane configuration device does not need to design and the cooperating of other functional material layers, so its preparation selectivity increases greatly, nearly all technology that is used to prepare organic semiconductor thin-film can be used for preparing light-sensitive material, such as solution casting, spin coating, lift, method such as roller coating, printing, self assembly, thermal evaporation.
The organic infrared or ultraviolet photovoltaic detector technology of plane configuration of the present invention both can prepare organic infrared semiconductor photovoltaic detector of plane configuration, can prepare plane configuration organic ultraviolet semiconductor photovoltaic detector again, it for optical waveguide detector, have response speed fast, low in energy consumption, be easy to form array, need not advantages such as biasing.Device of the present invention in addition have cost low, be easy to realize that large tracts of land light-sensitive material resistivity is controlled, need not refrigeration, can realize characteristics such as flexible processing so to have important potential using value at military, civil and some specific areas.
Conclusion is got up, and outstanding advantage of the present invention is:
1. substrate is alternative big, can prepare the photovoltaic type organic semiconductor detector that ultraviolet light (infrared light) is had response on amorphous glass, quartz, polycrystalline ceramics and the flexible plastic substrate of silicon chip, cheapness;
2. the plane configuration photovoltaic detector can effectively be avoided other functional layer or electrode pair response wave band absorption of electromagnetic wave or reflection;
3. be easy to realize large tracts of land, low cost, batch process;
4. the light-sensitive material preparation method is various, can be with solution casting, spin coating, lift, method preparations such as roller coating, printing, self assembly, thermal evaporation.
Description of drawings
Fig. 1 is the ultra-violet absorption spectrum and the chemical constitution thereof of organic ultraviolet semiconductor fluorenes.
Fig. 2 is the near-infrared absorption spectrum and the chemical constitution thereof of organic infrared semiconductor phthalocyanine rare earth.
Fig. 3 is the organic infrared or ultraviolet photovoltaic semiconductor detector schematic diagram of planar annular configuration.
Fig. 4 is the organic infrared or ultraviolet photovoltaic semiconductor detector schematic diagram of interdigitated plane configuration.
Fig. 5 is the organic infrared or ultraviolet photovoltaic semiconductor detector schematic diagram of stripe-shape plane configuration.
1 is substrate among the figure, the 2nd, and organic ultraviolet (infrared) semiconductor, 3 and 4 is the end (height) work function electrode.
Embodiment
Embodiment 1:
As shown in Figure 3, with the quartz plate is substrate 1, uses the method for thermal evaporation to deposit the thick organic ultraviolet semiconductor anthracene 2 of 1 μ m on quartz substrate, uses the method for thermal evaporation to deposit high work content Au outer ring electrode 4 on the anthracene film by mask plate, wherein Huan width is 500nm, and the Au film thickness is 300nm.Equally, use mask plate and accurate technique of counterpoint to deposit ring electrode 3 in the low work content yttrium with the method for thermal evaporation on the anthracene film, wherein Huan width is 500nm, and the yttrium film thickness is 300nm.
Embodiment 2:
As shown in Figure 4, with the quartz plate is substrate 1, method with magnetron sputtering deposits the high work function metal Au film of 500nm on quartz substrate, on the Au film, carry out whirl coating, preceding baking, exposure, development, post bake, etching again, remove photoresist, form the interdigital right electrode 4 of gold, prepare the interdigital left electrode 3 of low work function metal yttrium that thickness is 500nm with lift-off photolithography process again, luxuriant and rich with fragrance with the cyclohexane dissolving, draw luxuriant and rich with fragrance cyclohexane solution with dropper, it is dripped on the interdigital electrode, treat to make luxuriant and rich with fragrance thickness reach 500nm after the solvent evaporates.
Embodiment 3:
As shown in Figure 5, with the sheet glass is substrate 1, method with thermal evaporation deposits the thick organic infrared semiconductor iodine doping phthalocyanine erbium 2 of 1 μ m on glass substrate, use the method for thermal evaporation on iodine doping phthalocyanine erbium film, to deposit the right strip shaped electric poles 4 of high work content Au by mask plate, wherein the width of Au bar is 500nm, the length of Au bar is 2.5 μ m, and the Au film thickness is 300nm; Equally, use mask plate and accurate technique of counterpoint to deposit low work content yttrium left side strip shaped electric poles 3 with the method for thermal evaporation on iodine doping phthalocyanine erbium film, the width of yttrium bar is 500nm, and the length of yttrium bar is 2.5 μ m, and the yttrium film thickness is 300nm.
Embodiment 4:
With the pottery is substrate, method with thermal evaporation deposits the thick organic ultraviolet semiconductor phenanthrene of 1 μ m on ceramic substrate, use the method for thermal evaporation to deposit high work content strip Au electrode, Au film thickness 250nm on luxuriant and rich with fragrance film by mask plate, the width of Au bar is 500nm, and the length of Au bar is 2.5 μ m.Use mask plate and accurate technique of counterpoint to deposit low work content Nb strip shaped electric poles with the method for thermal evaporation on luxuriant and rich with fragrance film then, the Nb film thickness is 250nm, and two strip shaped electric poles spacings are 500nm, and the width of Nb bar is 500nm, and the length of Nb bar is 2.5 μ m.
Embodiment 5:
With the quartz is substrate, method with thermal evaporation deposits the thick organic infrared semiconductor phthalocyanine gadolinium of 1 μ m on quartz substrate, use the method for thermal evaporation on phthalocyanine gadolinium film, to deposit the right strip shaped electric poles of high work content Au by mask plate, wherein the width of Au bar is 1 μ m, the length of Au bar is 2.5 μ m, and the Au film thickness is 300nm.Equally, use mask plate and accurate technique of counterpoint to deposit low work content yttrium left side strip shaped electric poles with the method for thermal evaporation on phthalocyanine gadolinium film, the width of yttrium bar is 1 μ m, and the length of yttrium bar is 2.5 μ m, and the yttrium film thickness is 300nm.Two electrode spacing 500nm.
Embodiment 6:
With the pottery is substrate, method with magnetron sputtering deposits the high work function metal Au film of 500nm on ceramic substrate, on the Au film, carry out whirl coating, preceding baking, exposure, development, post bake, etching again, remove photoresist, form the interdigital right electrode of gold, prepare the interdigital left electrode of low work function metal yttrium that thickness is 500nm with lift-off photolithography process again.With chloroform dissolving phthalocyanine erbium, the chloroformic solution with dropper absorption phthalocyanine erbium drips to it on interdigital electrode, makes the thickness of phthalocyanine erbium reach 500nm.
Embodiment 7:
With the sheet glass is substrate, with the poly-fluorenes of the method organic ultraviolet semiconductor that spin coating 1 μ m is thick on glass substrate of spin coating, use the method for thermal evaporation on poly-fluorenes film, to deposit the right strip shaped electric poles of high work content Au by mask plate, wherein the width of Au bar is 500nm, the length of Au bar is 2.5 μ m, and the Au film thickness is 300nm.Equally, use mask plate and accurate technique of counterpoint to deposit low work content yttrium left side strip shaped electric poles with the method for thermal evaporation on poly-fluorenes film, the width of yttrium bar is 500nm, and the length of yttrium bar is 2.5 μ m, and the yttrium film thickness is 300nm.
Embodiment 8:
With the flexible substrate Merlon is substrate, method with magnetron sputtering deposits the high work function metal Au of 200nm on polycarbonate substrate, carry out whirl coating, preceding baking, exposure, development, post bake, etching, remove photoresist at Au again, form the interdigital right electrode of gold, prepare the interdigital left electrode of low work function metal yttrium that thickness is 200nm with lift-off photolithography process again.Carrying out the polymer of printing anthracene on the Merlon of electrode with ink-jet printer.
Above-described embodiment is only in order to illustrate technological thought of the present invention and characteristics; its purpose is to make those of ordinary skill in the art can understand content of the present invention and implements according to this; yet; scope of the present invention is not limited to this above-mentioned specific embodiment; be that the disclosed spirit of all foundations and equal variation or the modification done still are encompassed in protection scope of the present invention.
Claims (10)
1. the organic infrared photovoltaic semiconductor detector of plane configuration comprises: substrate (1), organic infrared semiconductor (2), low work function electrode (3,4) and high work function electrode (3,4) is characterized in that low work function electrode and high work function electrode are positioned at same plane.
2. a plane configuration organic ultraviolet photovoltaic semiconductor detector comprises: substrate (1), organic ultraviolet semiconductor (2), low work function electrode (3,4) and high work function electrode (3,4) is characterized in that low work function electrode and high work function electrode are positioned at same plane.
3. as claim 1 or the organic infrared or ultraviolet photovoltaic semiconductor detector of 2 described plane configurations, it is characterized in that said high work function electrode and low work function electrode are in same plane looping or interdigitation or spiral type or bar shaped or snakelike.
4. as claim 1 or the organic infrared or ultraviolet photovoltaic semiconductor detector of 2 described plane configurations, it is characterized in that said substrate (1) comprises Si base substrate; Amorphous glass, quartz substrate; Polycrystalline ceramics substrate and flexible plastic substrate.
5. the organic infrared photovoltaic semiconductor detector of plane configuration as claimed in claim 1 is characterized in that said organic infrared semiconductor (2) comprises that phthalocyanine erbium, phthalocyanine gadolinium etc. are near infrared light has the phthalocyanine rare earth with sandwich structure, dithiol alkene platinum, the graphite of photoelectric respone rare, graphene oxide etc. has photoelectric respone to infrared light material.
6. plane configuration organic ultraviolet photovoltaic semiconductor detector as claimed in claim 2 is characterized in that said organic ultraviolet semiconductor layer (2) comprising: anthracene, phenanthrene, fluorenes and be the derivative of parent with them or be polymer of monomers with they and they derivative.
7. as claim 1 or the organic infrared or ultraviolet photovoltaic semiconductor detector of 2 described plane configurations, it is characterized in that said organic infrared semiconductor or organic ultraviolet semi-conducting material (2) comprise the organic semiconducting materials of donor doping or acceptor doping.
8. as claim 1 or the organic infrared or ultraviolet photovoltaic semiconductor detector of 2 described plane configurations, it is characterized in that said low work function electrode (3,4) comprises Na, Ag, Mg, Al, Zn, Ti, Cd, Ca, K, Li, U, In, Cs, Gd, Hf, La, Mn, Nb, Pb, V, Zr electrode, and the single or multiple lift alloying metal electrode that is combined to form by them.
9. as claim 1 or the organic infrared or ultraviolet photovoltaic semiconductor detector of 2 described plane configurations, it is characterized in that said high work content top electrode material (3,4) comprises Au, Cu, Cr, Ni, Co, C, Si, Pd, Pt, Se, ITO, AZO, Fe, Ir, Os, and the composite material that is combined to form by them.
10. method for preparing the organic infrared or ultraviolet photovoltaic semiconductor detector of claim 1 or 2 described plane configurations is characterized in that said electrode can use thermal evaporation, magnetron sputtering, pulsed laser deposition, the independent technology of electron beam evaporation or combination technique preparation.
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| CN102931353A (en) * | 2012-10-25 | 2013-02-13 | 浙江大学 | High-responsivity visible blind organic UVB (ultraviolet b) optical detector |
| CN102969450A (en) * | 2012-11-20 | 2013-03-13 | 溧阳市生产力促进中心 | Ultraviolet detector |
| CN102997991A (en) * | 2012-11-20 | 2013-03-27 | 溧阳市生产力促进中心 | Ultraviolet detection device |
| CN105355795A (en) * | 2015-12-01 | 2016-02-24 | 电子科技大学 | Photoelectric detector array manufacture method based on conjugated polymer nanometer crystal lamination type self-assembling function film |
| CN108493339A (en) * | 2017-10-30 | 2018-09-04 | 上海幂方电子科技有限公司 | UV sensor and preparation method thereof |
| CN110739359A (en) * | 2019-10-23 | 2020-01-31 | 昆明物理研究所 | α -phase GeTe wide-spectrum infrared detector and preparation method thereof |
| CN112629674A (en) * | 2020-12-17 | 2021-04-09 | 华东师范大学 | Graphene oxide assisted infrared thermopile detector |
| CN114582994A (en) * | 2022-03-04 | 2022-06-03 | 仲恺农业工程学院 | Ultra-wide forbidden band amorphous MgGaO vacuum ultraviolet photovoltaic detector |
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| CN102931353A (en) * | 2012-10-25 | 2013-02-13 | 浙江大学 | High-responsivity visible blind organic UVB (ultraviolet b) optical detector |
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| CN105355795A (en) * | 2015-12-01 | 2016-02-24 | 电子科技大学 | Photoelectric detector array manufacture method based on conjugated polymer nanometer crystal lamination type self-assembling function film |
| CN108493339A (en) * | 2017-10-30 | 2018-09-04 | 上海幂方电子科技有限公司 | UV sensor and preparation method thereof |
| CN110739359A (en) * | 2019-10-23 | 2020-01-31 | 昆明物理研究所 | α -phase GeTe wide-spectrum infrared detector and preparation method thereof |
| CN112629674A (en) * | 2020-12-17 | 2021-04-09 | 华东师范大学 | Graphene oxide assisted infrared thermopile detector |
| CN114582994A (en) * | 2022-03-04 | 2022-06-03 | 仲恺农业工程学院 | Ultra-wide forbidden band amorphous MgGaO vacuum ultraviolet photovoltaic detector |
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