CN103311439A - Thin film photoconductive detector and manufacturing method and application thereof - Google Patents
Thin film photoconductive detector and manufacturing method and application thereof Download PDFInfo
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Abstract
The invention discloses a thin film photoconductive detector and a manufacturing method and application thereof. The thin film photoconductive detector comprises a substrate, a carrier transport layer, an electrode layer and a light absorption layer from bottom to top, wherein the electrode layer consists of an anode layer and a cathode layer positioned on the same layer. The detector integrates high migration ratio of an inorganic material and high light absorptivity of an organic material; when light irradiates onto an organic layer of a photoelectric device, the uppermost organic material layer absorbs light to generate carriers; and by virtue of energy level difference between an inorganic layer and the organic layer and the concentration difference of the carriers, the photo-generated carriers enter the inorganic material layer and can be fast collected by electrodes, thereby having large G and R values. Meanwhile, due to high migration rate of the inorganic material, the light current response time and the fall time of the device are greatly shortened, and therefore the sensitivity of the thin film photoconductive device is improved; and the thin film photoconductive detector has an important application value.
Description
Technical field
The present invention relates to a kind of film light photoconductive detector and preparation method thereof and application.
Background technology
At present, known photoconductive detector structure is comprised of two horizontal electrodes and middle light-sensitive layer.Photoconductive device is connected into the loop and adds a bias field, when incident light contacts with detector, the light-sensitive layer of detector inside produces electron hole pair, electron hole pair separates under the effect of electric field and collect to be formed photoelectric current by electrode, characterizes light intensity and size can be used for carrying out the directions such as light detection, image imaging or bio-sensing by the photoelectricity strength of flow.Therefore device is quite important to the susceptibility of light, and we characterize such Species sensitivity: responsiveness R and optical gain G with two important parameters usually.R represents a ratio of the luminous intensity of the photoelectric current that produces and introducing, and what G represented is the electric charge that photonic device inside of the every absorption of device is flow through.
These two values can represent with following formula:
(EQE is outer quantum effect, and λ is lambda1-wavelength, and h is Planck's constant, and c is the light velocity, and q is the quantity of electric charge, and L is device channel length (two interelectrode distance), and E is the electric field strength that adds, μ
nElectron mobility, μ
pBe hole mobility, τ is the life-span of photoexciton, t
nElectron transit time and t
pIt is the hole transit time)
Enough large G and R value are that photoconductive device is needed, some present devices mainly are on the 1-dimention nano device architecture, because: thus nanostructure has large specific area and surface to exist a large amount of deep energy levels to stick life-span that electric charge can strengthen photoexciton, thus the one-dimentional structure dimension that can reduce exciton diffusion transit time of reducing exciton increases R and G simultaneously.Up to the present, be that organic or inorganic 1-dimention nano device has all obtained very high G and R value.But comparatively speaking, it is more practical that film photoelectric is led device, and be more prone to simple and large tracts of land prepares.But the G of thin-film device and R value are very little with respect to the 1-dimention nano device, and this has limited their development.The reason that G and R value are little mainly is to be that the traditional devices structure can not overcome the shortcoming of material itself.For organic assembly, because there is material that low dielectric constant is arranged, the combination of exciton can be very large, and at normal temperatures, such exciton binding energy can not separate.The heterojunction structure to the receptor body combination that afterwards development is used a large amount of separates a large amount of free photo-generated carriers to the receptor body interface by introducing.Having brought like this another large impact is exactly that network structure in the heterojunction has increased exciton two interelectrode propagation distances, has caused low-down exciton transition rate.Therefore, find out that by formula (1), (2) G and R can be very low.For inorganic device, inorganic material has very high mobility, but its absorptivity is low especially, makes thin-film device that a very low EQE be arranged.It is the extinctions that improve inorganic material that a lot of work are arranged now.Utilize quantum skin effect and the dimensional effect of quantum dot can make inorganic material absorb more light, can represent large R and G value based on the photoelectric device of quantum dot, but also can be far short of what is expected with respect to the 1-dimention nano device performance.Therefore, it is the direction of making great efforts now that the film photoelectric that utilizes simple method to prepare high R and G value is led device.
Summary of the invention
The purpose of this invention is to provide a kind of film light photoconductive detector and preparation method thereof and application.
Film light photoconductive detector provided by the invention comprises substrate, carrier blocking layers, electrode layer and light-absorption layer from the bottom to top successively;
Described electrode layer is comprised of the anodal layer and the negative electrode layer that are positioned at same layer, and described anodal layer is 10-1000 μ m with the level interval of negative electrode layer, is specially 80 μ m.
Above-mentioned detector also can only be comprised of above-mentioned each layer.
Wherein, the material that consists of described flexible substrates is selected from least a in polyimides and the polyester film;
The relative molecular mass of described polyimides is 10000-100000g/mol, is specially 45000g/mol;
The relative molecular mass of described polyester is 10000-100000g/mol, is specially 70000g/mol.
The material that consists of described carrier blocking layers is selected from least a in zinc oxide, titanium oxide and the Graphene;
The thickness of described carrier blocking layers is 10-200nm, is specially 50nm.
The material that consists of described electrode layer is selected from least a in aluminium, gold, zinc and the silver;
The thickness of described electrode layer is 30-200nm, is specially 50nm.
The material that consists of described light-absorption layer is selected from least a in light-absorbing polymeric and the little molecule of extinction;
Described light-absorbing polymeric specifically is selected from least a among P3HT, PBDTTT-C and the PTB7; The relative molecular mass of described P3HT is 40000g/mol; The relative molecular mass of described PBDTTT-C is 40000～80000g/mol, is specially 60000g/mol; The relative molecular mass of described PTB7 is 10000～60000g/mol;
The little molecule of described extinction is specially PCBM; The relative molecular mass of described PCBM is 910.88g/mol;
The structural formula of P3HT, PBDTTT-C, PTB7 and PCBM as shown in Figure 3.
The thickness of described light-absorption layer is 50-200nm, is specially 150nm.
The method of the described detector of preparation provided by the invention comprises the steps:
1) prepares carrier blocking layers in described substrate;
2) prepare electrode layer at described carrier blocking layers;
3) prepare light-absorption layer at described electrode layer, obtain described detector.
In the said method, the method for preparing described carrier blocking layers, electrode layer and light-absorption layer is conventional method, concrete optional in spin-coating method, ink-jet printing process and vacuum vapour deposition any one;
In the described spin-coating method, mainly can be for the preparation of carrier blocking layers and light-absorption layer, the concentration of used solution is 1-100mg/ml, is specially 40mg/ml; The speed of spin coating is 500-10000rpm, is specially 1000rpm;
In the described ink-jet printing process, mainly can be for the preparation of carrier blocking layers, electrode layer and light-absorption layer, the concentration of ink is 1-100mg/ml, is specially 20mg/ml;
In the described sputtering method, mainly can be for the preparation of carrier blocking layers and electrode layer, the vacuum degree of sputter is 10
-4-10
-5Pa is specially 1 * 10
-4Pa;
In the described vacuum vapour deposition, mainly can be for the preparation of carrier blocking layers, electrode layer and light-absorption layer, the vacuum degree of evaporation carrier blocking layers or electrode layer is 10
-4-10
-5Pa is specially 1 * 10
-4Pa;
The vacuum degree of evaporation light-absorption layer is 10
-5-10
-6Pa is specially 1 * 10
-5Pa.
In step 1) before, also can first substrate be done following preliminary treatment: deionized water is successively used in described substrate, and acetone and isopropyl alcohol clean, again oven dry.
In addition; the detector that the invention described above provides also belongs to protection scope of the present invention in preparation at least a application and contain photodetector, image imaging device and the biology sensor of described detector in photodetector, image imaging device and the biology sensor.Wherein, described incident light is selected from least a in ultraviolet light, visible light, infrared light and the X-ray.
The present invention has overcome existing film light photoconductive detector R and the low-down deficiency of G value, provide a kind of simple in structure, the preparation method is easy, have the double-deck film light photoconductive detector of organic inorganic hybridization of very high responsiveness and optical gain.The structure of this detector is the organic inorganic hybridization double-decker, utilizes organic material extinction inorganic material transmission charge carrier, is clipped in the middle electrode of two layers of material and can have collected electricity and the hole.Because the extinction of organic material is very strong, very high external quantum efficiency is just arranged, and inorganic material has very strong carrier mobility so that the transit time of exciton reduces, simultaneously double-decker has increased the quantity that the probability of recombination that extra interface can reduce photo-generated carrier has also increased charge carrier, the photo-detector that above-mentioned reason makes has very large optical gain, thereby has improved the responsiveness of photo-detector to light.
This detector combines the high mobility of inorganic material and the high extinction of organic material, when illumination is mapped on the organic layer of photoelectric device, the organic material extinction of the superiors produces charge carrier, because the energy level difference between organic layer and inorganic layer and the concentration difference of charge carrier, photo-generated carrier enters inorganic material layer, thus and very fast very large G and the R value of being collected by electrode.Simultaneously, because the high mobility of inorganic material, photocurrent response time and the die-away time of the device that makes also reduce greatly, thereby have improved the sensitivity of thin film light guide device.
Description of drawings
Fig. 1 is the structural representation that film photoelectric is led sensitive detection parts.
Fig. 2 is the ESEM structural map of device architecture.
Fig. 3 is the chemical structural formula (P3HT, PBDTTT-C, PTB7 and PCBM) of organic light absorbent among the embodiment.
Fig. 4 is the abosrption spectrogram of used zinc oxide and organic material among the embodiment 1.
Fig. 5 is the comparison diagram of the mobility of used zinc oxide and organic material among the embodiment 1.
Fig. 6 be among the embodiment 1 photogenerated current with the variation diagram of zinc oxide mobility.
Fig. 7 is organic material single layer device and the comparison diagram of organic material inorganic material bi-layer devices photocurrent response time and die-away time among the embodiment 1.
Fig. 8 is the comparison diagram that organic material single layer device and organic material inorganic material bi-layer devices R value and G value change with applied voltage among the embodiment 1.
Fig. 9 be among the embodiment 1 organic material single layer device and organic material inorganic material bi-layer devices R value with the comparison diagram of the variation of monochromatic wavelength.
Figure 10 is the absorption spectrum comparison diagram of P3HT:PCBM, PBDTTT-C:PCBM and PTB7:PCBM among the embodiment 2.
Figure 11 is the comparison diagram that the relation of organic material inorganic material bi-layer devices R and wavelength among the embodiment 2 changes with the variation of organic material.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described raw material all can get from open commercial sources if no special instructions.
P3HT is available from Luminescence Technology Corporation company, and production code member is LT-S909;
PBDTTT-C is available from Luminescence Technology Corporation company, and production code member is LT-S981;
PTB7 is available from 1-material company, and production code member is OS0007;
PCBM is available from Luminescence Technology Corporation company, and production code member is LT-S905.
Embodiment 1,
1) as shown in Figure 1, zinc acetate is dissolved in the methyl cellosolve solution that obtains 40mg/ml concentration, 1000rpm spin coating 60s be on the substrate of glass 5 of 3mm at thickness and the 500 ℃ of 1h that anneal to obtain thickness be the carrier blocking layers 4 of 50nm.
The material that consists of carrier blocking layers is zinc oxide;
2) in step 1) the anodal layer 2 of gained carrier blocking layers difference vacuum evaporation and negative electrode layer 2, anodal and negative pole length is 8800 μ m, two interelectrode distance 80 μ m, the vacuum degree during vacuum evaporation is 1 * 10
-4Pa.
Consisting of the anodal layer of material with negative electrode layer all is aluminium;
Thickness is 50nm;
3) in step 2) on the anodal layer of gained and the negative electrode layer spin coating prepare one deck light-absorption layer, concrete steps comprise: be the P3HT of 40000g/mol and PCBM that relative molecular mass is 910.88g/mol with behind 1: 1 mixing of weight ratio with relative molecular mass, be dissolved in the solution that obtains 40mg/ml concentration in the o-dichlorohenzene, behind the 1000rpm spin coating 60s with 100 ℃ of 10min of substrate annealing, obtaining thickness is the light-absorption layer 3 of 150nm, obtains film light photoconductive detector provided by the invention;
Be illustrated in figure 2 as the ESEM structural map of this detector.
During test this detector is linked to each other with external circuit 6.Testing used light source is the tungsten halogen lamp white light source, and light intensity is 0.25mW/cm
2, the light intensity of used monochromatic source is 10.6 μ W/cm
2. all light intensity are calibrated by irradiatometer before test.The added bias voltage of the test of all optical detections is 10V.The used substrate of the test of mobility is Si/SiO
2, wherein Si is N-shaped heavy doping, SiO
2Thick 300nm, electric capacity are 10nF.
Be illustrated in figure 4 as the absorption spectrum comparison diagram of zinc oxide and P3HT: PCBM, zinc oxide has absorption and extinction seldom at ultraviolet light, and P3HT:PCBM has very strong very wide absorption in the ultraviolet-visible district.Simultaneously because the zinc oxide extinction is very low, thus its single layer device not with discussion.
Be illustrated in figure 5 as the test comparison figure of the mobility of zinc oxide and P3HT:PCBM, zinc oxide be electron transport material, its mobility is much larger than the mobility of P3HT:PCBM.
Photogenerated current as shown in Figure 6 is linear with the zinc oxide mobility, can prove that photogenerated current mainly is that zinc oxide film plays a carrier transport in the zinc oxide film transmission, and the zinc oxide mobility is larger, and the photogenerated current that device produces is just larger.
As shown in Figure 7, be in contrast individual layer P3HT:PCBM device (not having the ZnO layer) and the photocurrent response time of double-deck ZnO/P3HT:PCBM device provided by the invention and the comparison diagram of die-away time.Because the high mobility of ZnO, photocurrent response time and the die-away time of the device that makes also reduce greatly, thereby have improved the sensitivity of thin film light guide device.
Be illustrated in figure 8 as the comparison diagram of organic material single layer device and organic material inorganic material bi-layer devices R value and G value.Under identical condition, detector provided by the invention, its device performance is compared with conventional monolayers device architecture display performance, and G and R have obviously improved four to five orders of magnitude, and can compare with the performance of monodimension nanometer material.
Be illustrated in figure 9 as organic material single layer device and organic material inorganic material bi-layer devices R value with the figure of the variation of wavelength.Under identical lambda1-wavelength, its device performance is compared with organic material single layer device performance, and G and R have also obviously improved four to five orders of magnitude, and can compare with the performance of monodimension nanometer material.
It should be noted that only entering from organic material layer of common test, when substrate was transparent material, light also can be injected from the substrate direction.
Embodiment 2,
According to the step of embodiment 1, only with step 3) replace with following steps:
3) in step 2) on the anodal layer of gained and the negative electrode layer spin coating prepare one deck light-absorption layer, concrete steps comprise: be the PBDTTT-C of 60000g/mol and PCBM that relative molecular mass is 910.88g/mol with behind 1: 1.5 mixing of weight ratio with relative molecular mass, be dissolved in the solution that obtains 40mg/ml concentration in the o-dichlorohenzene, behind the 1000rpm spin coating 60s with 100 ℃ of 10min of substrate annealing, obtaining thickness is the light-absorption layer 3 of 150nm, obtains film light photoconductive detector provided by the invention;
According to upper identical step, only with step 3) in used PBDTTT-C replace with the PTB7 that relative molecular mass is 10000～60000g/mol, also obtain another kind of film light photoconductive detector provided by the invention.
During test this detector is linked to each other with external circuit 6.The light intensity of testing used monochromatic source is 10.6 μ W/cm
2. all light intensity are calibrated by irradiatometer before test.The added bias voltage of the test of all optical detections is 10V.
Be the absorption spectrum comparison diagram of P3HT:PCBM, PBDTTT-C:PCBM and PTB7:PCBM as shown in figure 10.P3HT:PCBM, PBDTTT-C:PCBM and PTB7:PCBM have very strong very wide absorption in the ultraviolet-visible district, and they have different absorption regions.
Be the R of organic material inorganic material bi-layer devices and the relation of wavelength as shown in figure 11.Contrast Figure 10, organic material extinction that visible film light photoconductive detector provided by the invention mainly is the upper strata produces charge carrier, and it changes the response of the optical wavelength variation with organic material.
Claims (10)
1. a film light photoconductive detector comprises substrate, carrier blocking layers, electrode layer and light-absorption layer from the bottom to top successively;
Described electrode layer is comprised of the anodal layer and the negative electrode layer that are positioned at same layer, and described anodal layer is 10-1000 μ m with the level interval of negative electrode layer.
2. detector according to claim 1 is characterized in that: the material that consists of described substrate is selected from least a in glass, silicon and the flexible substrates;
The material that consists of described flexible substrates is selected from least a in polyimides and the polyester film;
The relative molecular mass of described polyimides is 10000-100000g/mol, is specially 45000g/mol;
The relative molecular mass of described polyester is 10000-100000g/mol, is specially 70000g/mol.
3. detector according to claim 1 and 2 is characterized in that: the material that consists of described carrier blocking layers is selected from least a in zinc oxide, titanium oxide and the Graphene;
The thickness of described carrier blocking layers is 10-200nm, is specially 50nm.
4. arbitrary described detector according to claim 1-3 is characterized in that: the material that consists of described electrode layer is selected from least a in aluminium, gold, zinc and the silver;
The thickness of described electrode layer is 30-200nm, is specially 50nm.
5. arbitrary described detector according to claim 1-4 is characterized in that: the material that consists of described light-absorption layer is selected from least a in light-absorbing polymeric and the little molecule of extinction;
Described light-absorbing polymeric specifically is selected from least a among P3HT, PBDTTT-C and the PTB7;
The little molecule of described extinction is specially PCBM;
The thickness of described light-absorption layer is 50-200nm, is specially 150nm.
6. a method for preparing the arbitrary described detector of claim 1-5 comprises the steps:
1) prepares carrier blocking layers in described substrate;
2) prepare electrode layer at described carrier blocking layers;
3) prepare light-absorption layer at described electrode layer, obtain described detector.
7. method according to claim 6 is characterized in that: the method for preparing described carrier blocking layers, electrode layer and light-absorption layer all is selected from any one in spin-coating method, ink-jet printing process, sputtering method and the vacuum vapour deposition;
In the described sputtering method, the vacuum degree of sputter is 10
-4-10
-5Pa is specially 1 * 10
-4Pa;
In the described vacuum vapour deposition, the vacuum degree of evaporation carrier blocking layers and electrode layer is 10
-4-10
-5Pa is specially 1 * 10
-4Pa; The vacuum degree of evaporation light-absorption layer is 10
-5-10
-6Pa is specially 1 * 10
-5Pa.
8. the arbitrary described detector of claim 1-5 at least a application in preparation photodetector, image imaging device and biology sensor.
9. the photodetector, image imaging device and the biology sensor that contain the arbitrary described detector of claim 1-5.
10. application according to claim 8 or device claimed in claim 9 is characterized in that: described incident light is selected from least a in ultraviolet light, visible light, infrared light and the X-ray.
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