CN105118921B - A kind of organic photodetector of high external quantum efficiency and wide spectrum response and preparation method thereof - Google Patents
A kind of organic photodetector of high external quantum efficiency and wide spectrum response and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of organic photodetector of high external quantum efficiency and wide spectrum response, including be sequentially connected with：Lower conversion coating, substrate, anode, electron injection barrier layer, electron transfer layer, active layer and negative electrode；Wherein the thickness on electron injection barrier layer is 1 nanometer to 10 nanometers；The thickness of electron transfer layer is at 5 nanometers to 60 nanometers；The thickness of active layer is at 5 nanometers to 200 nanometers；The thickness of negative electrode is 50 nanometers to 1000 nanometers.The present invention equally realizes higher photomultiplication effect (EQE using the electron tunneling injection at the hole enhancing electrode after exciton dissociation>, and the structure is also advantageous to realize the organic photodetector part of wide spectrum response 15000%).
Description
Technical field
The present invention relates to a kind of organic photodetector, what more particularly to a kind of high external quantum efficiency and wide spectrum were responded has
Machine photodetector and preparation method thereof.
Background technology
Organic photodetector is because with flexible, cheap and many merits such as be easily integrated, it will be in consumer electronics
Product, home appliances, Intelligent building lighting, industry, production safety, health care and life science, environment, toy and education neck
Domain has a wide range of applications.In order to meet the requirement of practical application, organic photodetector should have high external quantum efficiency
Wider spectral response range.At present, the spectral response range of organic photodetector part is also narrow.In ultraviolet band,
Because glass and ITO absorb ultraviolet light, cause response of the device in DUV area smaller；In near infrared band, due to length
The more difficult separation of wave band exciton, thus device near infrared band external quantum efficiency also than relatively low.Therefore, how to be rung in wide spectrum
While answering, realize that higher external quantum efficiency has become the difficult point that organic photodetector is studied at present, refer here to material
Material selection and device structure design problem.
General organic photodetector generally includes anode, the organic layer of negative electrode and folder between two electrodes.It is organic
Layer can be the mixed layer of one layer of pure organic material or two or more organic materials, can also be a kind of donor
The double-decker of material and acceptor material composition.In order to improve the performance of device, it can also increase some on the both sides of these layers and repair
Adorn layer.
The important parameter of organic photodetector includes external quantum efficiency, bandwidth, dark-state current density and normalization detection
Rate.According to different types of application, the need for having difference to the performance of organic photodetector.This requires us as far as possible
The structure and selection suitable material of ground optimised devices, prepare the device with high combination property, can so meet more
The need for many applications.
From the point of view of material selected angle, organic semiconductor has preferable extinction characteristic to ultraviolet light and visible ray, therefore
Research to organic material is concentrated mainly in the synthesis of narrow band gap near infrared absorbing materials., Perzon et al. synthesis in 2007
Go out polymer LBPP-1, absorbed well and with good photoelectric characteristic, the spectrum of device because it has near infrared region
Response range can reach 1200nm, but the external quantum efficiency of device is low, and its maximum external quantum efficiency is only 10%.2009,
Yao et al. synthesizes a kind of novel polymer material PTT, although spectral response range decreases, but the outer quantum of device
Efficiency has large increase, and its external quantum efficiency at 850nm wavelength is up to 38%.2010, Forrest researchs were combined into
Go out Porphyrin-Tape and near infrared photodetector part is prepared as near-infrared responsive materials, its spectral response range can be with
More than 1400nm, external quantum efficiency can reach 6.5% in 1350nm.
And for device, primarily directed to structure design, preparation and the raising device that device is responded with wide spectrum
More researchs have been carried out in terms of the normalized detectivity of part.In July, 2009, Forrest seminar exists《Nanometer bulletin》On
Report a kind of hybrid photodetector of wide spectrum response.The detector be using organic semiconductor small molecule,
Prepared by organic polymer and CNT phase hydridization, it is finally obtained to normalize in wave-length coverage from 400nm to 1450nm and visits
Survey rate is more than 1010Jones device.After two months, Heeger seminar exists《Science》Magazine, which is reported, says a kind of with width
The full stress-strain polymer light electric explorer of spectral response, not only the response range of device is reachable from 300nm to 1450nm, and device
Part can also keep 1012Jones normalized detectivity；In addition, the normalized detectivity in order to improve device, researcher
Also attempt to reduce dark current by introducing the method for implant blocking layer.Binda in 2011 etc. is by using can spin on polymers
Electronics is prevented as barrier layer from anode is injected into organic layer, while keeping external quantum efficiency to have slight decrease, into
The dark-state current density of device is reduced to a thirtieth original (2nA cm work(-2), but the device is at 750nm
EQE only has 20% or so.And for absorbing redder material such as PCPDTBT, the receipts in hole will be stopped by introducing barrier layer
Collection, the high normalization from 300nm to 1100nm realized by the method for introducing barrier layer was reported such as 2010 Gong
Detection degree wide spectrum organic photodetector part, although improve detectivity and line because dark-state current density reduces by three orders of magnitude
Property degree, but due to the introducing on barrier layer, the external quantum efficiency of device also has the reduction of nearly an order of magnitude.The drop of external quantum efficiency
It is low, it is meant that same light and then makes the design of detection circuit become difficult according to the reduction of the photoelectric current of lower generation.Therefore, how
It is that wide spectrum response organic photodetector part is wanted at present to realize high normalized detectivity and high external quantum efficiency simultaneously
One of key issue that emphasis is solved.
In order to realize the organic photodetector part with higher external quantum efficiency, introducing multiplier effect becomes one kind more
Effective method, the external quantum efficiency of such device can be much larger than 100%, while the normalization for being also beneficial to improve device is visited
Survey rate.And organic photodetector mainly realizes photomultiplication effect using two kinds of mechanism at present：A kind of mode is to utilize light
Carrier transport in raw exciton enhancing organic semiconductor is come what is realized, and the premise of this method is that to have electric current stream in the devices
Cross to form space limitation electric current, form multiplication current, such device by light-generated excitons are quenched to strengthen carrier transport again afterwards
The dark-state electric current of part needs to reach saturation, and dark-state electric current is difficult to control to obtain very little.For example, Campbell in 2009 etc. utilizes spin coating
Naphthalocyanine prepare the near-infrared organic photodetector part with multiplier effect, when device is operated in -5V
Reverse biased under, although gain of the device under 1000nm wavelength can reach 10 times, but its dark current is but close to 0.01A
cm-2, therefore it is difficult to realize the device of high normalized detectivity；Another way be using photo-generated carrier coordination electrode with it is organic
Interface is injected come what is realized, and this mode dark-state electric current is limited by injection, therefore can be by the very little of dark-state current control.
Wherein most representational is that Huang groups in 2012 exist《Nature Nanotechnology》A kind of novel hybride of upper report
UV photodetector part.The device shows the property of Schottky contacts in the dark state, and under light illumination, due to producing interface
Trap can cause band curvature, and then reduce injection barrier, so as to strengthen electric charge injection so that device shows ohm and connect
Tactile property.The device also maintains very low dark-state current density while high external quantum efficiency is obtained, device
Normalization detection degree has reached 3.4 × 1015Jones, or even than taller by ten to one the hundred of inorganic semiconductor photoelectric detector
Times.But because interface defect is produced by ZnO nanoparticle, and ZnO is wide band gap semiconducter, it only absorbs ultraviolet light,
Device can only be completed in the light absorbs of visible region and infrared light district by alternative semiconductor, therefore be difficult by this device
Response spectrum be made wide.
The content of the invention
The invention solves the problems that a kind of technical problem of the prior art having there is provided high external quantum efficiency and wide spectrum response
Machine detection of luminescence device and preparation method thereof.
In order to solve the above-mentioned technical problem, technical scheme is specific as follows：
A kind of organic photodetector of high external quantum efficiency and wide spectrum response, including be sequentially connected with：
Lower conversion coating, substrate, anode, electron injection barrier layer, electron transfer layer, active layer and negative electrode；Wherein
The thickness on electron injection barrier layer is 1 nanometer to 10 nanometers；The thickness of electron transfer layer is at 5 nanometers to 60 nanometers；
The thickness of active layer is at 5 nanometers to 200 nanometers；The thickness of negative electrode is 50 nanometers to 1000 nanometers；
The material of lower conversion coating is the organic semiconducting materials or inorganic photic hair of the luminescence generated by light with UV absorption
Luminescent material；The material on electron injection barrier layer is that the material acted on hole barrier is acted on electric transmission；Electron transfer layer
Material be the organic or inorganic material with electric transmission；The material of active layer is the mixture of organic material or comprising nothing
The organic material mixture of machine nano-particle.
In the above-mentioned technical solutions, the hole that thickness is 1 nanometer to 50 nanometers is additionally provided between active layer and negative electrode to note
Enter barrier layer；
The material of the hole implant blocking layer is to inject barrier effect with hole, has the material of electric transmission effect concurrently
Material.
In the above-mentioned technical solutions, the material of the lower conversion coating is 4P-NPB, Alq3Or TPBi.
In the above-mentioned technical solutions, the material on the electron injection barrier layer is TPBi, BmPypb, LiF or MgF2。
In the above-mentioned technical solutions, the donor and acceptor material of the active layer be SnPc and C60 or SnPc and C70,
Or SnNcCl2With C60 or SnNcCl2And C70；Wherein P-type material and n type material blended layer concentration 5-80% it
Between.
In the above-mentioned technical solutions, the material of the electron transfer layer is C60 or C70.
A kind of preparation method of the organic photodetector of above-mentioned high external quantum efficiency and wide spectrum response, including it is following
Step：
Anode on substrate is photo-etched into electrode；
Cleaning drying, is handled with oxygen plasma, and is toasted in vacuum drying oven；
It is transferred in vacuum coating system, when vacuum reaches requirement, is first deposited in the side without anode under one layer
Conversion coating, is deposited electron injection barrier layer, electron transfer layer, active layer and negative electrode on anode successively afterwards；
The evaporation rate control of electron injection barrier layer and electron transfer layer is per second per second to 0.3 nanometer at 0.05 nanometer；
The evaporation rate control of active layer is per second per second to 0.5 nanometer at 0.05 nanometer；The evaporation rate of negative electrode is controlled at 0.05 nanometer
It is per second per second to 2 nanometers；
The material of lower conversion coating is the organic semiconducting materials or inorganic photic hair of the luminescence generated by light with UV absorption
Luminescent material；The material on electron injection barrier layer is that the material acted on hole barrier is acted on electric transmission；Electron transfer layer
Material be the organic or inorganic material with electric transmission；The material of active layer is the mixture of organic material or comprising nothing
The organic material mixture of machine nano-particle；
The thickness on electron injection barrier layer is 1 nanometer to 10 nanometers；The thickness of electron transfer layer is at 5 nanometers to 60 nanometers；
The thickness of active layer is at 5 nanometers to 200 nanometers；The thickness of negative electrode is 50 nanometers to 1000 nanometers.
In the above-mentioned technical solutions, after active layer has been deposited, continue that the sky that a layer thickness is 1 nanometer to 50 nanometers is deposited
Cave implant blocking layer, then evaporation cathode again；
The material of the hole implant blocking layer is to inject barrier effect with hole, has the material of electric transmission effect concurrently
Material；
The evaporation rate control of the hole implant blocking layer is per second per second to 0.3 nanometer at 0.05 nanometer.
The present invention has following beneficial effect：
First, the device in the present invention strengthens the electron tunneling at electrode by using the hole after exciton dissociation under light state
Higher photoelectric current multiplier effect is realized in injection, to improve the external quantum efficiency of device, so as to enhance detectivity；Its
It is secondary, due to selecting SnPc, SnNcCl2, vulcanized lead, the low bandgap material such as porphyrin is used as active layer so that it is in wider light
Light can be effectively absorbed in spectral limit, so as to greatly widen response range of the device near infrared region；Finally, upper conversion
Layer helps to change into the ultraviolet light for being difficult to penetrate glass into the visible ray for readily penetrating through glass, forms exciton afterwards and produces photoelectricity
Stream, so that device possesses higher external quantum efficiency in ultraviolet region.The maximum feature of the structure is to combine above-mentioned three kinds
Means, finally realize the multiplication type organic photodetector responded with wide spectrum, its external quantum efficiency and spectral response model
Enclose and all improve a lot.
The present invention equally realizes higher light using the electron tunneling injection at the hole enhancing electrode after exciton dissociation
Electric multiplier effect (EQE>, and the structure is also advantageous to realize the organic photodetector of wide spectrum response 15000%)
Part.PRELIMINARY RESULTS shows that the spectral response range of device can cover 300nm to 1000nm, and from mechanistic point, device
The spectral response range of part can also be widened further.Due to introducing lower transferring structure, device is enhanced in ultraviolet range
Response so that the response range of device can reach 250nm to 1200nm.
Brief description of the drawings
The present invention is described in further detail with reference to the accompanying drawings and detailed description.
Fig. 1 be the present invention high external quantum efficiency and wide spectrum response organic photodetector energy level schematic diagram.
The structural representation for the organic photodetector that Fig. 2 responds for the high external quantum efficiency and wide spectrum of the present invention.
Fig. 3 is the high external quantum efficiency in embodiment 1 and the external quantum efficiency of the organic photodetector of wide spectrum response
Curve.
The response of the device for the organic photodetector that Fig. 4 responds for the high external quantum efficiency and wide spectrum in embodiment 1
Degree and normalized detectivity curve.
Fig. 5 is the high external quantum efficiency in embodiment 2 and the external quantum efficiency of the organic photodetector of wide spectrum response
Curve.
The response of the device for the organic photodetector that Fig. 6 responds for the high external quantum efficiency and wide spectrum in embodiment 2
Degree and normalized detectivity curve.
Fig. 7 is the high external quantum efficiency in embodiment 3 and the external quantum efficiency of the organic photodetector of wide spectrum response
Curve.
The response of the device for the organic photodetector that Fig. 8 responds for the high external quantum efficiency and wide spectrum in embodiment 3
Degree and normalized detectivity curve.
Fig. 9 is the high external quantum efficiency in embodiment 4 and the external quantum efficiency of the organic photodetector of wide spectrum response
Curve.
The response of the device for the organic photodetector that Figure 10 responds for the high external quantum efficiency and wide spectrum in embodiment 4
Degree and normalized detectivity curve.
Figure 11 is the high external quantum efficiency in embodiment 5 and the external quantum efficiency of the organic photodetector of wide spectrum response
Curve.
The response of the device for the organic photodetector that Figure 12 responds for the high external quantum efficiency and wide spectrum in embodiment 5
Degree and normalized detectivity curve.
Reference in figure is expressed as：
Conversion coating, 2- substrates, 3- anodes, 4- electron injections barrier layer, 5- electron transfer layers, 6- active layers, 7- are empty under 1-
Cave implant blocking layer, 8- negative electrodes.
Embodiment
The present invention invention thought be：
The present invention devises a kind of organic photodetector part with lower transferring structure, and then strengthens device in deep ultraviolet
The response in area, and strengthen the electron tunneling method for implanting at electrode to improve the outer of device by using the hole after exciton dissociation
Quantum efficiency, finally prepares the wide spectrum response organic photodetector part with high external quantum efficiency.
The present invention device used lower conversion and doubling technology, using the hole accummulation after exciton dissociation under light state come
Strengthen the electron tunneling injection at electrode and realize higher photoelectric current multiplier effect, to improve the external quantum efficiency of device, so that
Strengthen the detectivity of device, and by selecting suitable material system and effective device structure design to widen device
Spectral response range, the device shows high external quantum efficiency and the characteristics of wide spectrum is responded.
The present invention is described in detail below in conjunction with the accompanying drawings.
Lower conversion coating 1 can be the organic fluorescence materials with luminescence generated by light, organic phosphorescent material and inorganic light-emitting material
Material；
Substrate 2 can be glass or flexible polymer transparent substrates；
Anode 3 can be tin indium oxide (ITO) or conducting polymer or other transparency electrodes, and work function is arrived in 4.7eV
5.2eV；
Electron injection barrier layer 4 can be with electric transmission act on and hole barrier act on material, such as TPBi and
The organic materials such as Bmpypb and LiF and MgF2Etc. inorganic material；
Electron transfer layer 5 can be the organic or inorganic material with electric transmission；
Active layer 6 is the mixture of organic material or the organic material mixture comprising inorganic nano-particle；
Hole implant blocking layer 7 can inject barrier effect with hole, have the material of electric transmission effect concurrently；
Negative electrode 8 can be metallic aluminium or other metals or other electrodes.
The preparation method of the organic photodetector of high external quantum efficiency and the wide spectrum response of the present invention is as follows：
Ito anode 3 on ito glass is first photo-etched into the electrode of fine strip shape, then cleaned, nitrogen drying, with oxygen etc. from
Daughter is handled 1 to 5 minute, and toasts 30 minutes to one hours at 110 degrees Celsius in vacuum drying oven, and then it is transferred to
In vacuum coating system, treat that vacuum reaches 1 to 5 × 10-4During handkerchief, first without ITO sides be deposited one layer under convert layer material, it
Electron injection barrier layer 4, electron transfer layer 5, active layer 6, hole implant blocking layer 7 and negative electrode 8 is deposited on the ito layer successively afterwards
Composition, two of which electrode intersect part formed device effective light detecting area, its effective area be 16 square millimeters, electricity
The thickness of sub- implant blocking layer 4 be 1 nanometer to 10 nanometers, the thickness of electron transfer layer 5 at 5 nanometers to 60 nanometers, active layer 6
Thickness is at 5 nanometers to 200 nanometers, and the thickness of hole implant blocking layer 7 is 1 nanometer to 50 nanometers, and the thickness of negative electrode 8 arrives for 50 nanometers
1000 nanometers.
Doping concentration in active layer 6 is by weight control：P-type material and n type material blended layer concentration in 5-
Between 80%.
The evaporation rate on electron injection barrier layer 4, electron transfer layer 5 and hole implant blocking layer 7 is controlled at 0.05 nanometer
Per second per second to 0.3 nanometer, the evaporation rate of active layer 6 controls, the steaming of negative electrode 8 per second per second to 0.5 nanometer at 0.05 nanometer
Send out speed control per second per second to 2 nanometers at 0.05 nanometer.
It is organic that the high external quantum efficiency and wide spectrum for illustrating the present invention below with multiple embodiments are responded
Photodetector and preparation method thereof.
Embodiment 1:
The ito anode 3 in glass substrate 2 is first photo-etched into 4 mm wides, 30 millimeters of long electrodes, then cleaned, nitrogen blows
It is dry, the glass is placed into vacuum drying oven and toasted at 110 degrees Celsius 30 minutes, afterwards, is handled 2 minutes with oxygen plasma,
Afterwards, the glass is put into vacuum coating system.When vacuum coating system vacuum reaches 1 to 5 × 10-4When handkerchief, first
There is no ITO sides that one layer of 4P-NPB is deposited in glass, electron injection barrier layer 4 (TPBi) is deposited on the ito layer successively afterwards, electricity
Sub- transport layer 5 (C70), active layer 6 (SnPc and C70 mixed layers), hole implant blocking layer 7 (BCP) and negative electrode 8 (Al), wherein
Two electrodes intersect part formed device effective light detecting area, its effective area be 16 square millimeters, implant blocking layer 4
Thickness be 3 nanometers, the thickness of electron transfer layer 5 is 20 nanometers, and the thickness of active layer 6 is 80 nanometers, hole implant blocking layer 7
Thickness is 10 nanometers, and the thickness of negative electrode 8 is 100 nanometers.Doping concentration in active layer 6 (SnPc by volume:C70) control exists
5%.The final structure that is prepared into is 4P-NPB/Glass/ITO/TPBi/C70/SnPc:C70/BCP/Al wide spectrum response is organic
Photodetector.
The external quantum efficiency that accompanying drawing 3 gives the organic photodetector of this high external quantum efficiency and wide spectrum response is bent
Line, maximum external quantum efficiency of the device under -10 V biass can reach 3300%, and the spectral response range of device can be from
250 nanometers to 1000 nanometers.Accompanying drawing 4 gives the responsiveness and normalized detectivity curve of device, under -10 V biass, device
The responsiveness of part can reach 24 amperes every watt, and the normalized detectivity of device is up to 1012Jones.Device in this embodiment
Maximum feature be that device has high external quantum efficiency and wide spectral response range.
Embodiment 2:
The ito anode 3 in glass substrate 2 is first photo-etched into 4 mm wides, 30 millimeters of long electrodes, then cleaned, nitrogen blows
It is dry, the glass is placed into vacuum drying oven and toasted at 110 degrees Celsius 30 minutes, afterwards, is handled 2 minutes with oxygen plasma,
Afterwards, the glass is put into vacuum coating system.When vacuum coating system vacuum reaches 1 to 5 × 10-4When handkerchief, first
There is no ITO sides that one layer of 4P-NPB is deposited in glass, electron injection barrier layer 4 (TPBi) is deposited on the ito layer successively afterwards, electricity
Sub- transport layer 5 (C70), active layer 6 (SnPc and C70 mixed layers), hole implant blocking layer 7 (BCP) and negative electrode 8 (Al), wherein
Two electrodes intersect part formed device effective light detecting area, its effective area be 16 square millimeters, implant blocking layer 4
Thickness be 3 nanometers, the thickness of electron transfer layer 5 is 20 nanometers, and the thickness of active layer 6 is 80 nanometers, hole implant blocking layer 7
Thickness is 10 nanometers, and the thickness of negative electrode 8 is 100 nanometers.Doping concentration in active layer 6 is controlled 25% by volume.Finally
Structure is prepared into for 4P-NPB/Glass/ITO/TPBi/C70/SnPc:C70/BCP/Al wide spectrum response organic photoelectric detection
Device.
The external quantum efficiency that accompanying drawing 5 gives the organic photodetector of this high external quantum efficiency and wide spectrum response is bent
Line, maximum external quantum efficiency of the device under -10 V biass can reach 10000%, and the spectral response range of device can be from
250 nanometers to 1000 nanometers.Accompanying drawing 6 gives the responsiveness and normalized detectivity curve of device, under -10 V biass, device
The responsiveness of part can reach 70 amperes every watt, and the normalized detectivity of device is up to 1012Jones.Device in this embodiment
Maximum feature be that device has high external quantum efficiency and wide spectral response range.
Embodiment 3:
The ito anode 3 in glass substrate 2 is first photo-etched into 4 mm wides, 30 millimeters of long electrodes, then cleaned, nitrogen blows
It is dry, the glass is placed into vacuum drying oven and toasted at 110 degrees Celsius 30 minutes, afterwards, is handled 2 minutes with oxygen plasma,
Afterwards, the glass is put into vacuum coating system.When vacuum coating system vacuum reaches 1 to 5 × 10-4When handkerchief, first
There is no ITO sides that one layer of 4P-NPB is deposited in glass, electron injection barrier layer 4 (TPBi) is deposited on the ito layer successively afterwards, electricity
Sub- transport layer 5 (C70), active layer 6 (SnPc and C70 mixed layers), hole implant blocking layer 7 (BCP) and negative electrode 8 (Al), wherein
Two electrodes intersect part formed device effective light detecting area, its effective area be 16 square millimeters, implant blocking layer 4
Thickness be 3 nanometers, the thickness of electron transfer layer 5 is 20 nanometers, and the thickness of active layer 6 is 80 nanometers, hole implant blocking layer 7
Thickness is 10 nanometers, and the thickness of negative electrode 8 is 100 nanometers.Doping concentration SnPc in active layer 6:C70 is controlled by volume
80%.The final structure that is prepared into is 4P-NPB/Glass/ITO/TPBi/C70/SnPc:C70/BCP/Al wide spectrum response has
Machine photodetector.
The external quantum efficiency that accompanying drawing 7 gives the organic photodetector of this high external quantum efficiency and wide spectrum response is bent
Line, maximum external quantum efficiency of the device under -10 V biass can reach 5000%, and the spectral response range of device can be from
250 nanometers to 1000 nanometers.Accompanying drawing 8 gives the responsiveness and normalized detectivity curve of device, under -10 V biass, device
The responsiveness of part can reach 35 amperes every watt, and the normalized detectivity of device is up to 1012Jones.Device in this embodiment
Maximum feature be that device has high external quantum efficiency and wide spectral response range.
Embodiment 4:Electron injection barrier layer 4 uses LiF
The ito anode 3 in glass substrate 2 is first photo-etched into 4 mm wides, 30 millimeters of long electrodes, then cleaned, nitrogen blows
It is dry, the glass is placed into vacuum drying oven and toasted at 110 degrees Celsius 30 minutes, afterwards, is handled 2 minutes with oxygen plasma,
Afterwards, the glass is put into vacuum coating system.When vacuum coating system vacuum reaches 1 to 5 × 10-4When handkerchief, first
There is no ITO sides that one layer of 4P-NPB is deposited in glass, electron injection barrier layer 4 (LiF) is deposited on the ito layer successively afterwards, electricity
Sub- transport layer 5 (C70), active layer 6 (SnPc and C70 mixed layers), hole implant blocking layer 7 (BCP) and negative electrode 8 (Al), wherein
Two electrodes intersect part formed device effective light detecting area, its effective area be 16 square millimeters, implant blocking layer 4
Thickness be 3 nanometers, the thickness of electron transfer layer 5 is 20 nanometers, and the thickness of active layer 6 is 80 nanometers, hole implant blocking layer 7
Thickness is 10 nanometers, and the thickness of negative electrode 8 is 100 nanometers.Doping concentration in active layer 6 is controlled 25% by volume.Finally
Structure is prepared into for 4P-NPB/Glass/ITO/LiF/C70/SnPc:C70/BCP/Al wide spectrum response organic photoelectric detection
Device.
The external quantum efficiency that accompanying drawing 9 gives the organic photodetector of this high external quantum efficiency and wide spectrum response is bent
Line, maximum external quantum efficiency of the device under -10 V biass can reach 10000%, and the spectral response range of device can be from
250 nanometers to 1000 nanometers.Accompanying drawing 10 gives the responsiveness and normalized detectivity curve of device, under -10 V biass, device
The responsiveness of part can reach 70 amperes every watt, and the normalized detectivity of device is up to 1012Jones.Device in this embodiment
Maximum feature be that device has high external quantum efficiency and wide spectral response range.
Embodiment 5:Electron transfer layer 5 uses C60
The ito anode 3 in glass substrate 2 is first photo-etched into 4 mm wides, 30 millimeters of long electrodes, then cleaned, nitrogen blows
It is dry, the glass is placed into vacuum drying oven and toasted at 110 degrees Celsius 30 minutes, afterwards, is handled 2 minutes with oxygen plasma,
Afterwards, the glass is put into vacuum coating system.When vacuum coating system vacuum reaches 1 to 5 × 10-4When handkerchief, first
There is no ITO sides that one layer of 4P-NPB is deposited in glass, electron injection barrier layer 4 (TPBi) is deposited on the ito layer successively afterwards, electricity
Sub- transport layer 5 (C60), active layer 6 (SnPc and C60 mixed layers), hole implant blocking layer 7 (BCP) and negative electrode 8 (Al), wherein
Two electrodes intersect part formed device effective light detecting area, its effective area be 16 square millimeters, implant blocking layer 4
Thickness be 3 nanometers, the thickness of electron transfer layer 5 is 20 nanometers, and the thickness of active layer 6 is 80 nanometers, hole implant blocking layer 7
Thickness is 10 nanometers, and the thickness of negative electrode 8 is 100 nanometers.Doping concentration in active layer 6 is controlled 25% by volume.Finally
Structure is prepared into for 4P-NPB/Glass/ITO/TPBi/C60/SnPc:C60/BCP/Al wide spectrum response organic photoelectric detection
Device.
The external quantum efficiency that accompanying drawing 11 gives the organic photodetector of this high external quantum efficiency and wide spectrum response is bent
Line, maximum external quantum efficiency of the device under -10 V biass can reach 10000%, and the spectral response range of device can be from
250 nanometers to 1000 nanometers.Accompanying drawing 12 gives the responsiveness and normalized detectivity curve of device, under -10 V biass, device
The responsiveness of part can reach 70 amperes every watt, and the normalized detectivity of device is up to 1012Jones.Device in this embodiment
Maximum feature be that device has high external quantum efficiency and wide spectral response range.
Embodiment 6:Electron injection barrier layer 4 uses BmPypb, and active layer 6 uses SnNcCl2With C60 mixed layers
The ito anode 3 in glass substrate 2 is first photo-etched into 4 mm wides, 30 millimeters of long electrodes, then cleaned, nitrogen blows
It is dry, the glass is placed into vacuum drying oven and toasted at 110 degrees Celsius 30 minutes, afterwards, is handled 2 minutes with oxygen plasma,
Afterwards, the glass is put into vacuum coating system.When vacuum coating system vacuum reaches 1 to 5 × 10-4When handkerchief, first
There is no ITO sides that one layer of 4P-NPB is deposited in glass, electron injection barrier layer 4 (BmPypb) be deposited on the ito layer successively afterwards,
Electron transfer layer 5 (C60), (SnNcCl of active layer 62With C60 mixed layers), hole implant blocking layer 7 (BCP) and negative electrode 8 (Al),
Two of which electrode intersect part formed device effective light detecting area, its effective area be 16 square millimeters, injection resistance
The thickness of barrier 4 is 1 nanometer, and the thickness of electron transfer layer 5 is 5 nanometers, and the thickness of active layer 6 is 5 nanometers, and hole injection stops
7 thickness of layer are 1 nanometer, and the thickness of negative electrode 8 is 100 nanometers.Doping concentration in active layer 6 is controlled 45% by volume.Most
Structure is prepared into eventually for 4P-NPB/Glass/ITO/BmPypb/C60/SnNcCl2:C60/BCP/Al wide spectrum response is organic
Photodetector.
Maximum external quantum efficiency of the device under -10 V biass can reach 5500%, and the spectral response range of device can
With from 250 nanometers to 1200 nanometers.
Embodiment 7:Electron injection barrier layer 4 uses MgF2, active layer 6 uses SnNcCl2With C70 mixed layers
The ito anode 3 in glass substrate 2 is first photo-etched into 4 mm wides, 30 millimeters of long electrodes, then cleaned, nitrogen blows
It is dry, the glass is placed into vacuum drying oven and toasted at 110 degrees Celsius 30 minutes, afterwards, is handled 2 minutes with oxygen plasma,
Afterwards, the glass is put into vacuum coating system.When vacuum coating system vacuum reaches 1 to 5 × 10-4When handkerchief, first
There is no ITO sides that one layer of 4P-NPB is deposited in glass, (the MgF of electron injection barrier layer 4 is deposited on the ito layer successively afterwards2), electricity
Sub- transport layer 5 (C60), (SnNcCl of active layer 62With C70 mixed layers), hole implant blocking layer 7 (BCP) and negative electrode 8 (Al), its
In two electrodes intersect part formed device effective light detecting area, its effective area be 16 square millimeters, injection stop
The thickness of layer 4 is 10 nanometers, and the thickness of electron transfer layer 5 is 60 nanometers, and the thickness of active layer 6 is 200 nanometers, hole injection resistance
The thickness of barrier 7 is 50 nanometers, and the thickness of negative electrode 8 is 100 nanometers.Doping concentration in active layer 6 is controlled 65% by volume.
The final structure that is prepared into is 4P-NPB/Glass/ITO/MgF2/C60/SnNcCl2:C70/BCP/Al wide spectrum responds organic light
Electric explorer.
Maximum external quantum efficiency of the device under -10 V biass can reach 8000%, and the spectral response range of device can
With from 250 nanometers to 1200 nanometers.
Donor material used in the present invention can be the material of other high hole mobilities, and this material need to expire
Foot row condition：Its highest is occupied track (HOMO) between 4.0eV and 4.8eV, and the minimum track (LUMO) that do not occupy exists
Between 5.5eV and 8eV.
Active layer can also be combined and high performance photoelectricity is made using three kinds or more than three kinds materials in the present invention
Detector.
The hole implant blocking layer 7 of device in the present invention is not essential, and can not also be used.
The following is the full name and molecular structural formula of above-mentioned used material
1、4P-NPB：Full name 4P-NPB, N, N'-di- (1-naphthalenyl)-N, N'-diphenyl- [1,1':4',
1'':4
2、Alq3：Chinese：8-hydroxyquinoline aluminium
3、TPBi：Chinese：1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene
4、BmPypb：English name：1,3-bis(3,5-dipyrid-3-yl-phenyl)benzene
5、LiF：Chinese lithium fluoride
6、C60：Chinese：Fullerene C20
7、C70：Chinese：Fullerene C70
8、SnPc：Chinese：Tin Phthalocyanine (II)
9、SnNcCl2：English name:Tin naphthalocyanine dichloride
9、ITO：Tin indium oxide
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (8)
1. a kind of high external quantum efficiency and the organic photodetector of wide spectrum response, it is characterised in that including what is be sequentially connected with：
Lower conversion coating (1), substrate (2), anode (3), electron injection barrier layer (4), electron transfer layer (5), active layer (6) and the moon
Pole (8)；Wherein
The thickness on electron injection barrier layer (4) is 1 nanometer to 10 nanometers；The thickness of electron transfer layer (5) is received at 5 nanometers to 60
Rice；The thickness of active layer (6) is at 5 nanometers to 200 nanometers；The thickness of negative electrode (8) is 50 nanometers to 1000 nanometers；
The material of lower conversion coating (1) is organic semiconducting materials of the luminescence generated by light with UV absorption or with UV absorption
Luminescence generated by light inorganic fluorescent substances；The material on electron injection barrier layer (4) is with electric transmission effect and hole
The material of barrier effect；The material of electron transfer layer (5) is the organic or inorganic material with electric transmission；Active layer (6)
Material is the mixture of organic material or the organic material mixture comprising inorganic nano-particle.
2. high external quantum efficiency according to claim 1 and the organic photodetector of wide spectrum response, it is characterised in that
The hole implant blocking layer (7) that thickness is 1 nanometer to 50 nanometers is additionally provided between active layer (6) and negative electrode (8)；
The material of the hole implant blocking layer (7) is to inject barrier effect with hole, has the material of electric transmission effect concurrently.
3. high external quantum efficiency according to claim 1 and the organic photodetector of wide spectrum response, it is characterised in that
The material of the lower conversion coating (1) is 4P-NPB, Alq3Or TPBi.
4. high external quantum efficiency according to claim 1 and the organic photodetector of wide spectrum response, it is characterised in that
The material of the electron injection barrier layer (4) is TPBi, BmPypb, LiF or MgF2。
5. high external quantum efficiency according to claim 1 and the organic photodetector of wide spectrum response, it is characterised in that
The donor and acceptor material of the active layer (6) are SnPc and C60 or SnPc and C70 or SnNcCl2With C60 or
SnNcCl2And C70；Wherein P-type material and n type material in the concentration of blended layer between 5-80%.
6. high external quantum efficiency according to claim 1 and the organic photodetector of wide spectrum response, it is characterised in that
The material of the electron transfer layer (5) is C60 or C70.
7. a kind of preparation method of the organic photodetector of high external quantum efficiency and wide spectrum response described in claim 1,
It is characterised in that it includes following steps：
Anode (3) on substrate (2) is photo-etched into electrode；
Cleaning drying, is handled with oxygen plasma, and is toasted in vacuum drying oven；
It is transferred in vacuum coating system, when vacuum reaches requirement, is first deposited one layer lower turn in the side without anode (3)
Change layer (1), is deposited electron injection barrier layer (4) on anode (3) successively afterwards, electron transfer layer (5), active layer (6) and the moon
Pole (8)；
The evaporation rate control of electron injection barrier layer (4) and electron transfer layer (5) is every at 0.05 nanometer per second to 0.3 nanometer
Second；The evaporation rate control of active layer (6) is per second per second to 0.5 nanometer at 0.05 nanometer；The evaporation rate control of negative electrode (8) exists
0.05 nanometer per second per second to 2 nanometers；
The material of lower conversion coating (1) is organic semiconducting materials of the luminescence generated by light with UV absorption or with UV absorption
Luminescence generated by light inorganic fluorescent substances；The material on electron injection barrier layer (4) is with electric transmission effect and hole
The material of barrier effect；The material of electron transfer layer (5) is the organic or inorganic material with electric transmission；Active layer (6)
Material is the mixture of organic material or the organic material mixture comprising inorganic nano-particle；
The thickness on electron injection barrier layer (4) is 1 nanometer to 10 nanometers；The thickness of electron transfer layer (5) is received at 5 nanometers to 60
Rice；The thickness of active layer (6) is at 5 nanometers to 200 nanometers；The thickness of negative electrode (8) is 50 nanometers to 1000 nanometers.
8. preparation method according to claim 7, it is characterised in that after active layer (6) has been deposited, continues to be deposited one layer
Thickness is 1 nanometer to 50 nanometers of hole implant blocking layer (7), then evaporation cathode (8) again；
The material of the hole implant blocking layer (7) is to inject barrier effect with hole, has the material of electric transmission effect concurrently；
The evaporation rate control of the hole implant blocking layer (7) is per second per second to 0.3 nanometer at 0.05 nanometer.
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| CN105655491B (en) * | 2016-03-29 | 2018-12-07 | 上海大学 | The organic solar batteries and preparation method thereof of integral type hole transmission layer with exciton blocking and sunlight enhanced sensitivity |
| CN106025070B (en) * | 2016-05-24 | 2018-11-27 | 北京交通大学 | Photomultiplier transit type organic photodetector with spectral selection and preparation method thereof |
| CN107331776B (en) * | 2017-07-18 | 2019-12-06 | 电子科技大学 | Novel organic near-infrared photoelectric detector based on charge transfer compound |
| CN107591484B (en) * | 2017-09-01 | 2019-09-24 | 北京交通大学 | A kind of multiplication type organic photodetector having both narrowband and broadband light detectivity |
| CN108807683B (en) * | 2018-07-05 | 2021-04-30 | 南京邮电大学 | Wide-spectral-response multiplication type organic photoelectric detector |
| CN114284436A (en) * | 2021-12-21 | 2022-04-05 | 广州光达创新科技有限公司 | Organic-inorganic hybrid short-wave infrared photoelectric detector, array formed by same and related preparation method |
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| JP2011238762A (en) * | 2010-05-10 | 2011-11-24 | Kyoto Univ | Photoelectric conversion element |
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| JPH0198266A (en) * | 1987-10-12 | 1989-04-17 | Ricoh Co Ltd | Photoelectric converter element |
| JP2011238762A (en) * | 2010-05-10 | 2011-11-24 | Kyoto Univ | Photoelectric conversion element |
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