CN100553006C - Organic ultraviolet optical sensor based on phosphorescence material light diode - Google Patents

Organic ultraviolet optical sensor based on phosphorescence material light diode Download PDF

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CN100553006C
CN100553006C CN 200710055787 CN200710055787A CN100553006C CN 100553006 C CN100553006 C CN 100553006C CN 200710055787 CN200710055787 CN 200710055787 CN 200710055787 A CN200710055787 A CN 200710055787A CN 100553006 C CN100553006 C CN 100553006C
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optical sensor
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CN101101970A (en
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李文连
孔治国
车广波
初蓓
毕德锋
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Changchun Institute of Optics Fine Mechanics and Physics of CAS
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Abstract

The invention belongs to the optical sensor technology field of ultraviolet light sensitivity, relate to a kind of organic ultraviolet optical sensor based on phosphorescence material light diode, adopt the compound that has existed as giving body with low ionization energy (IP) and high hole transmission characteristic, phosphorescent compound with high electron affinity (EA) and big electron transport property makes the material range of choice wideer as acceptor; Device is a sandwich construction, adopts the thermal evaporation film forming, and manufacture craft is simple, cost is low; And, make device volume little, in light weight owing to adopted thin organic layer and metal electrode layer; Because phosphor material has long lifetime of excited state and exciton diffusion length, thereby/polymer photovoltaic diode more organic than the fluorescent material have higher efficient promptly ultraviolet light to be had higher response sensitivity, and only responsive and be the blind area to visible light to the 300-400nm band ultraviolet.The present invention can be widely used in science, industry and commercial field.

Description

Organic ultraviolet optical sensor based on phosphorescence material light diode
Technical field
The invention belongs to the optical sensor technology field of ultraviolet light sensitivity, relate to a kind of organic ultraviolet optical sensor based on the phosphor material organic diode.
Background technology
Organic material photon-electronic switch requires the exciton that optical absorption produces is resolved into electric charge carrier, and this optical absorption is different with conventional solar cells, and the organic solar batteries optical absorption spectra requires the main visual field (400-700nm) that covers.The ultraviolet ray that solar irradiation is mapped to ground mainly is in the 300-400nm wave band, and the light that shines ground mainly is in visible light wave range, and it is that wave band is the ultraviolet light sensitivity of (300-400nm) that ultraviolet optical sensor then requires a small amount of ultraviolet.At present, ultraviolet optical sensor mainly is to adopt inorganic ultraviolet light Sensitive Apparatus as optical pickocff, its complicated process of preparation, and the cost height is not suitable for large-area applications; And the spectral response of much organic/polymer photovoltaic diode covers the visual field more and all be to adopt fluorescent material, if fluorescent material is as the ultraviolet light Sensitive Apparatus, because the diffusion length of their exciton is shorter, expection can be to the response sensitivity step-down of ultraviolet light.
Summary of the invention
At in the prior art mainly being the complicated process of preparation that adopts inorganic ultraviolet light Sensitive Apparatus to exist as optical pickocff, the spectral response of the problem that cost is high and organic/polymer photovoltaic diode covers the visual field more and all is to adopt fluorescent material, and fluorescent material is as the problem of ultraviolet light Sensitive Apparatus to the response sensitivity step-down of ultraviolet light, the invention provides a kind of organic ultraviolet optical sensor based on phosphorescence material light diode, the compound that adopts the high hole transmission characteristic with low ionization energy (IP) that has existed is as giving body, the phosphorescent compound of high electron transport property with high electron affinity (EA) makes the material range of choice wideer as acceptor; Device is a sandwich construction, adopts the thermal evaporation film forming, and manufacture craft is simple, cost is low; And, make device volume little, in light weight owing to adopted thin organic layer and metal electrode layer.
Technical scheme one: the present invention is a layer structure, to the electronic collection electrode layer, be followed successively by substrate, hole passive electrode layer, electron donor layer, electron donor and electron acceptor mixed layer, electron acceptor layer, electron collection layer, electronic collection electrode layer by substrate (UV-irradiation one side); The electron donor layer thickness is 5～20nm, the electron acceptor layer thickness is 20～40nm, electron donor and electron acceptor mixed layer thickness are 2-10nm, the material that electron donor adopts is diamine derivative (diamine derivative), the material that electron acceptor adopts is the complex of iridium, platinum, osmium or rhenium, and the weight ratio of electron donor material and electron acceptor material is 1: 1 in electron donor and the electron acceptor mixed layer; The material that the electron collection layer adopts is LiF or CsF, and the electron collection layer thickness is 0.8～3nm; The material that the electronic collection electrode layer adopts is Al, and the electronic collection electrode layer thickness is 100～150nm.
Technical scheme two: the present invention is a layer structure, to the electronic collection electrode layer, is followed successively by substrate, hole passive electrode layer, electron donor layer, electron acceptor layer, electron collection layer, electronic collection electrode layer by substrate (UV-irradiation one side); The electron donor layer thickness is 5～20nm, and the material that electron donor adopts is diamine derivative (diamine derivative); The electron acceptor layer thickness is 20～40nm, and the material that electron acceptor adopts is the complex of iridium, platinum, osmium or rhenium; The material that the electron collection layer adopts is LiF or CsF, and the electron collection layer thickness is 0.8～3nm; The material that the electronic collection electrode layer adopts is Al, and the electronic collection electrode layer thickness is 100～150nm.
Preparation method of the present invention: deposition electron donor layer on the passive electrode layer of hole; Deposition electron acceptor layer on the electron donor layer, perhaps the mixed layer of deposition one deck electron donor and electron acceptor on the electron donor layer deposits the electron acceptor layer more in the above, deposits electron collection layer, electronic collection electrode layer afterwards more successively; Above-mentioned each layer all adopts the thermal evaporation process deposits.
Substrate glass, the ITO nesa coating is selected in hole passive electrode layer (nesa coating) for use; The electron donor layer is selected TPD (N, N '-diphenyl-N, N '-bis (3-methylphenyl)-[1,1 '-biphenyl]-4,4 '-diamine) or m-MTDATA for use
(4,4 ', 4 "-tris (3-methylphenyl-phenylaminojtriphenylamine; ) material, thickness is chosen 5～20nm; The electron acceptor layer is selected Ir (ppy) for use 3: fac (tris～2-phenyl Pyridine) Iridium, or Btp 2Ir (acac): bis (2-(2 ' 8-benzo[4,5-a] thienyl) (pyridinato-N, C 3') iridium (acetylacetonate), thickness is chosen 20～40nm; In electron donor and the electron acceptor mixed layer, the weight ratio of electron donor and electron acceptor is 1: 1, and thickness is 2-10nm; The electron collection material layer select LiF or CsF for use, thickness adopts 0.8～3nm; The material of electronic collection electrode layer adopt Al or, thickness can adopt 100～150nm.
Making successful device is the 365nm UV-irradiation with the centre wavelength of known power earlier, change exposure intensity or range measurement and go out in the photovoltaic property signal of telecommunication open circuit voltage (Voc) or short circuit current (Jsc) with the irradiates light strength relationship and draw out calibration curve, detect the signal of telecommunication that unknown strength meter ultraviolet light obtains with ultraviolet optical sensor again and contrast the sensitivity that calculates ultraviolet light to be measured with calibration curve.
Beneficial effect: because phosphor material has long lifetime of excited state and exciton diffusion length, thereby the present invention more organic than the fluorescent material/the polymer photovoltaic diode has higher efficient promptly ultraviolet light to be had more high sensitivity, and is and only responsive and be the blind area to visible light to the 300-400nm band ultraviolet.
Compare as the ultraviolet optical sensor of optical pickocff with the inorganic ultraviolet light Sensitive Apparatus of prior art, the present invention has the following advantages:
(1) material source wide ranges
Because many holes of Organic Light Emitting Diode (OLED) are injected and hole mobile material has low IP value more and absorption is positioned at the 300-400 wave band, the many electric transmission phosphor materials that are used for OLED have high EA more and absorb and also are positioned at the 300-400 wave band, like this when choosing electron donor and electron acceptor material, as long as they are respectively good hole injection/hole mobile material and electron transport material, select both combinations just can construct ultraviolet optical sensor.Compare with inorganic material, do not need numerous and diverse material synthetic, by ionization energy and the electron affinity parameter that provides them, and phosphor material film absorption spectrum, even contain the ultraviolet light that is shorter than the 300nm wavelength, because device of the present invention all is to select the ITO electro-conductive glass for use, this glass can filter the ultraviolet light that is shorter than the 300nm wavelength and not make it enter sensor component, so just can select to be used for the material of OLED.
(2) manufacture craft is simple
Owing to adopt device architecture of the present invention to be and similar " sandwich " formula sandwich construction of many device architectures of OLED, all material all is to adopt vacuum thermal evaporation method film forming, does not need the semiconductor fabrication process of the necessary complexity of inorganic ultraviolet optical sensor device.
(3) volume is little, in light weight
Because the present invention has adopted thin organic layer and metal electrode layer, except the thickness (0.3-1.1mm) of hole passive electrode layer, the thickness of all functions layer is no more than 1 micron.
Organic ultraviolet optical sensor of the present invention can be widely used in science, industry and commercial field.
Description of drawings
Fig. 1 is a structural representation of the present invention, also is Figure of abstract.Among the figure 1, substrate, 2, hole passive electrode layer (nesa coating), 3, the electron donor layer, 4, electron donor and electron acceptor mixed layer, 5, the electron acceptor layer, 6, the electron collection layer, 7, the electronic collection electrode layer.
Fig. 2 is another technical scheme structural representation of the present invention.1, substrate, 2, hole passive electrode layer (nesa coating), 3, the electron donor layer, 5, the electron acceptor layer, 6, the electron collection layer, 7, the electronic collection electrode layer.
Embodiment:
The present invention will be further described below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
Technical scheme one:
Embodiment 1:
Select device architecture shown in Figure 1 for use: in the present embodiment, at first the ITO film on the hole passive electrode layer 2 selection glass substrate 1 is as nesa coating.After cleaning the nesa coating on the substrate 1, at first in high vacuum (3-2 * 10 -1Handkerchief) under, deposition one layer thickness is a 10nm electron donor layer 3 on nesa coating, and the material of electron donor layer 3 adopts TPD; Deposit the mixed layer 4 of electron donor and electron acceptor then on electron donor layer 3, thickness is 5nm, and electron donor material is TPD, and electron acceptor material is Ir (ppy) 3, TPD and Ir (ppy) 3Weight ratio be 1: 1; Deposit electron acceptor layer 5 again on the mixed layer 4 of electron donor and electron acceptor, the material of electron acceptor layer 5 is Ir (ppy) 3, thickness is chosen 20nm or 30nm or 40nm; Deposit electron collection layer 6 afterwards on electron acceptor layer 5, the material of electron collection layer 6 adopts LiF, and its thickness is 0.8nm; Deposit electronic collection electrode layer 7 at last on electron collection layer 6, electronic collection electrode layer 7 adopts metal A l materials, and thickness is 100nm.Above-mentioned all films all adopt the thermal evaporation process deposits.The thickness of each layer uses the film thickness monitoring instrument to monitor.Making successful device shines with the UV-irradiation agent of known power earlier, change exposure intensity or range measurement and go out in the photovoltaic property signal of telecommunication open circuit voltage (Voc) or short circuit current (Jsc) with the exposure intensity relation and draw out calibration curve, detect the signal of telecommunication of unknown strength meter ultraviolet light acquisition and the sensitivity that the calibration curve contrast calculates ultraviolet light to be measured with ultraviolet optical sensor again, the device of present embodiment detects ultraviolet light sensitivity and is: uv power to be measured is 0.017mW/cm 2The time, the I of ultraviolet optical sensor SCSignal is 1.8 μ A/cm 2
Embodiment 2:
ITO film on the hole passive electrode layer 2 selection glass substrate 1 is as nesa coating, and electron donor layer 3 is selected the m-MTDATA material for use, and its thickness is 6nm; Deposit the mixed layer 4 of electron donor and electron acceptor then on electron donor layer 3, thickness is 5nm, and the material of electron donor is m-MTDATA, and the material of electron acceptor is Btp 2Ir (acac), m-MTDATA and Btp 2The weight ratio of Ir (acac) is 1: 1; Deposit electron acceptor layer 5 again on the mixed layer 4 of electron donor and electron acceptor, electron acceptor layer 5 the selection of material are Btp 2Ir (acac), thickness choose 20nm or 30nm or 35nm; Deposit electron collection layer 6 afterwards on electron acceptor layer 5, electron collection layer 6 material adopt LiF, and its thickness is 0.8nm; Deposit electronic collection electrode layer 7 at last on electron collection layer 6, electronic collection electrode layer 7 adopts metal A l materials, and its thickness is 120nm.Above-mentioned each layer all adopts the thermal evaporation process deposits.The thickness of film uses the film thickness monitoring instrument to monitor.It is as follows to adopt embodiment 1 described method of measurement to record the result:
The present embodiment device detects ultraviolet light sensitivity: uv power to be measured is 0.009mW/cm 2The time, the I of ultraviolet optical sensor SCSignal is 1.0 μ A/cm 2
Embodiment 3:
ITO film on the hole passive electrode layer 2 selection glass substrate 1 is as nesa coating; Electron donor layer 3 is selected the m-MTDATA material for use, and thickness is 15nm; Mixed layer 4 thickness of electron donor and electron acceptor are 5nm, and electron donor material is selected m-MTDATA for use, and electron acceptor is selected Ir (ppy) for use 3, m-MTDATA and Ir (ppy) 3Weight ratio be 1: 1; Electron acceptor layer 5 is selected Ir (ppy) for use 3, thickness is chosen 20nm or 25nm or 30nm; Deposit electron collection layer 6 afterwards on electron acceptor layer 5, electron collection layer 6 material adopt LiF, and its thickness is 1.5nm; Deposit electronic collection electrode layer 7 at last on electron collection layer 6, electronic collection electrode layer 7 adopts metal A l materials, and its thickness is 120nm.
It is as follows to adopt embodiment 1 described method of measurement to record the result:
The present embodiment device detects ultraviolet light sensitivity: uv power to be measured is 0.010mW/cm 2The time, the I of ultraviolet optical sensor SCSignal is 1.6 μ A/cm 2
Embodiment 4:
ITO film on the hole passive electrode layer 2 selection glass substrate 1 is as nesa coating; Electron donor layer 3 is selected the m-MTDATA material for use, and thickness is 20nm, and the electron donor material of the mixed layer 4 of electron donor and electron acceptor is selected m-MTDATA for use, and electron acceptor is selected Btp for use 2Ir (acac), m-MTDATA and Btp 2Ir (acac) weight ratio is 1: 1, and the thickness of the mixed layer 4 of electron donor and electron acceptor is 7nm; Deposit electron acceptor layer 5 again on the mixed layer 4 of electron donor and electron acceptor, electron acceptor layer 5 is selected Btp for use 2Ir (acac), thickness choose 20nm or 25nm or 30nm; Deposit electron collection layer 6 afterwards on electron acceptor layer 5, electron collection layer 6 material adopt CsF, and its thickness is 2.5nm; Deposit electronic collection electrode layer 7 at last on electron collection layer 6, electronic collection electrode layer 7 adopts metal A l materials, and its thickness is 120nm.
Effect: it is as follows to adopt embodiment 1 described method of measurement to record the result:
The present embodiment device detects ultraviolet light sensitivity: uv power to be measured is 0.010mW/cm 2The time, the I of ultraviolet optical sensor SCSignal is 1.6 μ A/cm 2
Embodiment 5:
Hole passive electrode layer 2 selects the ITO film as nesa coating; Electron donor layer 3 the selection of material m-MTDATA thickness are 10nm; The electron donor material of the mixed layer 4 of electron donor and electron acceptor is selected m-MTDATA for use, and electron acceptor is selected Btp for use 2Ir (acac) and Ir (ppy) 3Mixture, Btp 2Ir (acac) and Ir (ppy) 3Weight ratio be 1: 1, m-MTDATA and Btp 2Ir (acac) and Ir (ppy) 3The weight ratio of mixture be 1: 1, the thickness of the mixed layer 4 of electron donor and electron acceptor is 10nm; Deposit electron acceptor layer 5 again on the mixed layer 4 of electron donor and electron acceptor, electron acceptor layer 5 is selected Btp for use 2Ir (acac) or Ir (ppy) 3Mixture, Btp 2Ir (acac) and Ir (ppy) 3Weight ratio be 1: 1, thickness is 20nm or 30nm or 40nm; Deposit electron collection layer 6 afterwards on electron acceptor layer 5, electron collection layer 6 material adopt CsF, and its thickness is 2.5nm; Deposit electronic collection electrode layer 7 at last on electron collection layer 6, electronic collection electrode layer 7 adopts metal A l materials, and its thickness is 150nm.Effect: it is as follows to adopt embodiment 1 described method of measurement to record the result:
The present embodiment device detects ultraviolet light sensitivity: uv power to be measured is 0.009mW/cm 2The time, the I of ultraviolet optical sensor SCSignal is 0.8 μ A/cm 2
Embodiment 6:
Select device architecture shown in Figure 1 for use: in the present embodiment, at first the ITO film on the hole passive electrode layer 2 selection glass substrate 1 is as nesa coating.After cleaning the nesa coating on the substrate 1, at first in high vacuum (5-1 * 10 -4Handkerchief) under, deposition one layer thickness is a 10nm electron donor layer 3 on nesa coating, and the material of electron donor layer 3 adopts TPD; Deposition electron acceptor layer 5 on electron donor layer 3, the material of electron acceptor layer 5 is Ir (ppy) 3, thickness is chosen 20nm or 30nm or 40nm; Deposit electron collection layer 6 afterwards on electron acceptor layer 5, the material of electron collection layer 6 adopts LiF, and its thickness is 0.8nm; Deposit electronic collection electrode layer 7 at last on electron collection layer 6, electronic collection electrode layer 7 adopts metal A l materials, and thickness is 100nm.Above-mentioned all films all adopt the thermal evaporation process deposits.The thickness of each layer uses the film thickness monitoring instrument to monitor.Make successful device earlier with the UV-irradiation agent irradiation of known power from, change exposure intensity or range measurement and go out in the photovoltaic property signal of telecommunication open circuit voltage (Voc) or short circuit current (Jsc) with the exposure intensity relation and draw out calibration curve, survey the signal of telecommunication of unknown strength meter ultraviolet light acquisition and the sensitivity that the calibration curve contrast calculates ultraviolet light to be measured with ultraviolet optical sensor again, the device of present embodiment detects ultraviolet light sensitivity and is: uv power to be measured is 0.017mW/cm 2The time, the I of ultraviolet optical sensor SCSignal is 1.8 μ A/cm 2

Claims (8)

1, a kind of organic ultraviolet optical sensor based on phosphorescence material light diode, it is characterized in that being layer structure, to the electronic collection electrode layer, be followed successively by substrate, hole passive electrode layer, electron donor layer, electron donor and electron acceptor mixed layer, electron acceptor layer, electron collection layer, electronic collection electrode layer by substrate; The electron donor layer thickness is 5～20nm, the electron acceptor layer thickness is 20～40nm, electron donor and electron acceptor mixed layer thickness are 2-10nm, the material that electron donor adopts is a diamine derivative, the material that electron acceptor adopts is the complex of iridium, platinum, osmium or rhenium, and the weight ratio of electron donor material and electron acceptor material is 1: 1 in electron donor and the electron acceptor mixed layer; The material that the electron collection layer adopts is LiF or CsF, and the electron collection layer thickness is 0.8～3nm; The material that the electronic collection electrode layer adopts is Al, and the electronic collection electrode layer thickness is 100～150nm.
2, a kind of organic ultraviolet optical sensor based on phosphorescence material light diode, it is characterized in that being layer structure, to the electronic collection electrode layer, be followed successively by substrate, hole passive electrode layer, electron donor layer, electron acceptor layer, electron collection layer, electronic collection electrode layer by substrate; The electron donor layer thickness is 5～20nm, and the material that electron donor adopts is a diamine derivative; The electron acceptor layer thickness is 20～40nm, and the material that electron acceptor adopts is the complex of iridium, platinum, osmium or rhenium; The material that the electron collection layer adopts is LiF or CsF, and the electron collection layer thickness is 0.8～3nm; The material that the electronic collection electrode layer adopts is Al, and the electronic collection electrode layer thickness is 100～150nm.
3, the organic ultraviolet optical sensor based on phosphorescence material light diode according to claim 1 and 2 is characterized in that electron donor material selects TPD or m-MTDATA for use; Electron acceptor material is selected Ir (ppy) for use 3Or Btp 2Ir (acac).
4, the organic ultraviolet optical sensor based on phosphorescence material light diode according to claim 1 and 2 is characterized in that the electron donor layer thickness is 10nm, 6nm, 15nm or 20nm.
5, the organic ultraviolet optical sensor based on phosphorescence material light diode according to claim 1, the mixed layer thickness that it is characterized in that electron donor and electron acceptor is 5nm, 7nm or 10nm.
6, the organic ultraviolet optical sensor based on phosphorescence material light diode according to claim 1 and 2 is characterized in that the electron acceptor layer thickness is 20nm, 30nm, 40nm, 25nm or 35nm.
7, the organic ultraviolet optical sensor based on phosphorescence material light diode according to claim 1 and 2 is characterized in that the electron collection layer thickness is 0.8nm, 1.5nm or 2.5nm.
8, the organic ultraviolet optical sensor based on phosphorescence material light diode according to claim 1 and 2 is characterized in that the electronic collection electrode layer thickness is 100nm, 120nm or 150nm.
CN 200710055787 2007-06-20 2007-06-20 Organic ultraviolet optical sensor based on phosphorescence material light diode Expired - Fee Related CN100553006C (en)

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CN102097593B (en) * 2010-12-02 2012-11-28 吉林大学 Organic solar battery having phosphorescent material-doped donor layer
CN102891256B (en) * 2011-07-18 2015-04-08 吉林师范大学 Cu(I) complex-based visible dead zone organic ultraviolet light detector
CN102891258B (en) * 2011-07-18 2015-07-08 吉林师范大学 Re(I) complex phosphor material-based organic light detector
CN102386335A (en) * 2011-12-12 2012-03-21 中国科学院长春光学精密机械与物理研究所 All-band reverse optical detector constructed on basis of organic small molecular material

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