CN106920882A - A kind of perovskite photodetector based on medium/medium/metal electrode and preparation method thereof - Google Patents
A kind of perovskite photodetector based on medium/medium/metal electrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of perovskite photodetector based on medium/medium/metal electrode and preparation method thereof, characterized in that, detector is constituted including transparent substrates, medium/medium/metal electrode, perovskite photosensitive layer, charge transport layer and reflecting electrode from bottom to top.By the thickness for adjusting front medium layer in medium/medium/metal electrode, metal level, rear dielectric layer, it is possible to achieve perovskite explorer response spectrum it is adjustable.Present invention, avoiding the use of ITO, rare indium resource is saved, reduced the preparation cost of detector.
Description
Technical field
The invention belongs to technical field of photoelectric detection, and in particular to a kind of perovskite based on medium/medium/metal electrode
Photodetector and preparation method thereof.
Background technology
Photodetector in optic communication, environmental monitoring, numerous necks of the military and national economy such as image sensing, infrared remote sensing
Domain has a wide range of applications.Photodetector has extensive use in the every field of military and national economy.In visible ray or near
Infrared band is mainly used in radionetric survey and detection, industry automatic control, Photometric Measurement etc.；It is mainly used in guided missile in infrared band
The aspects such as guidance, infrared thermal imaging, infrared remote sensing.Ultraviolet band is frequently utilized for the aspects such as detection, sterilization, UV detections.Always
It, photodetector is widely used in national economy with the every field of military affairs, with significant military value and warp
Ji value.Most photodetectors are all based on inorganic material making in the market.Organic inorganic hybridization perovskite
The advantages of material extinction coefficient is high, absorption region is wide, exciton diffusion length is long becomes and makes wide spectrum response detector
Excellent material.Compared with inorganic detector, perovskite organic inorganic hybridization detector has preparation process is simple, low cost, weight
The many merits such as amount is light, fast response time, market prospects are very wide.Meanwhile, with the fast development of intelligent movable equipment, thoroughly
The market of prescribed electrode rapidly increases.Tin-doped indium oxide (ITO) transparency electrode occupies the market share of the transparency electrode overwhelming majority.
But one side indium is a kind of scarce resource, the electric conductivity of difference is compeled under another aspect ITO fragility, the heat resistance of difference and large area
The people that promote for cutting develop the new transparency electrode that can replace ITO.Explorer response spectrum is adjustable for avoiding background radiation
Interference have great importance.Yet there are no the relevant report of the adjustable perovskite photodetector of response spectrum.
The content of the invention
For the deficiency in background technology, the present invention is using medium/medium/metal multilayer film as perovskite photodetection
The electrode of device, there is provided a kind of adjustable perovskite photodetector based on medium/medium/metal electrode of response spectrum and its
Preparation method.In order to achieve this, the technical solution adopted in the present invention is as follows：
A kind of perovskite photodetector based on medium/medium/metal electrode and preparation method thereof, it is characterised in that under
It is supreme to be constituted including transparent substrates, medium/medium/metal electrode, perovskite photosensitive layer, charge transport layer, reflecting electrode, device
Part preparation process is sequentially followed successively by and prepares medium/medium/metal electrode on a transparent substrate, in medium/medium/metal
Perovskite photosensitive layer is prepared on electrode, charge transport layer, the preparation reflection on charge transport layer are prepared on perovskite photosensitive layer
Electrode.
Further, described medium/medium/metal electrode is three-decker, including front medium layer and rear dielectric layer with
And the metal level being clipped in two layer medium layer is constituted；Its dielectric layer is MoO3、WoO3、PEDOT:PSS, ZnO or TiO2Thoroughly
One or two kinds of in bright conducting medium, metal level is the one kind in Ag, Al, Au, Cu.
Further, described perovskite photosensitive layer is CH3NH3PbX3Perovskite material, wherein X=Cl, Br, I or it
Mixture.
Further, when the rear dielectric layer in medium/medium/metal electrode is electron transport material, selection hole passes
One kind in defeated material NPB, TCTA, TAPC, CBP, P3HT, spiro-OMeTAD is used as charge transport layer；When medium/metal/
When rear dielectric layer in media electrode is hole mobile material, electric transmission class material C is selected60、C70、Bphen、BCP、Alq3、
One kind in PCBM is used as charge transport layer.
Further, described metallic reflective electrodes are Al, Ag or Au.
Further, the preparation of device is comprised the following steps：
(1) transparent substrates cleaning
Transparent substrates are successively using acetone, water, glass cleaner cleaning, and cleaning is each in isopropanol, deionized water, ethanol after finishing
Ultrasonically treated 15 minutes, dried up with high pure nitrogen after being disposed, be then placed within uviol lamp, irradiated 20 minutes；
(2) medium/medium/metal electrode is prepared
First, according to the difference of selected dielectric layer, on a transparent substrate by hot evaporation, rotary coating, magnetron sputtering, ALD etc.
Method deposits one layer of front medium layer, front medium layer thickness 10-50 nm；
Then, layer of metal layer, metal layer thickness 5- are grown by the method for hot evaporation or magnetron sputtering on front medium layer
50 nm；
Finally, dielectric layer after one layer of regrowth, front medium layer thickness 10-50 nm on the metal layer；
(3) perovskite photosensitive layer is prepared
One layer of perovskite photosensitive layer, perovskite light are prepared on medium/medium/metal electrode using solwution method or coevaporation method
The thickness of photosensitive layer is in 100-1000 nm；
(4) charge transport layer is prepared
According to the difference of selected charge transport materials, selection thermal evaporation deposition or spin coating method are deposited on perovskite photosensitive layer
One layer charge transport layer；Charge transport layer thickness is in 10-50 nm
(5) reflecting electrode is prepared
By the method deposition of reflective electrode of hot evaporation on charge transport layer, the preparation of device is completed.
Medium/medium/metal (medium/medium/metal) multilayer film transparency electrode tool that interference effect based on light is made
The good electric conductivity of standby metal, can be real by the regulation and control to medium/medium/metal electrode dielectric layer and the thickness of metal level
The selectivity of existing particular range wavelength is anti-reflection and increases anti-.Explorer response spectrum is adjustable to be had for the interference that avoids background radiation
Important meaning.Yet there are no the relevant report of the adjustable perovskite photodetector of response spectrum.Present invention use medium/
Medium/metal transparent conductive film as perovskite photodetector electrode, by medium/medium/metal electrode intermediary
The regulation and control of matter layer and metal level, construct the adjustable perovskite photodetector of response spectrum.Compared with prior art, the present invention
Beneficial effect at least include：(1) use of ITO is avoided, rare indium resource has been saved, being prepared into for device is reduced
This；(2) by the regulation to medium/medium/metal electrode dielectric layer and metal level, it is possible to achieve to special spectrum scope
Response, it is to avoid the interference of optical detection background radiation.
Brief description of the drawings
Fig. 1 is perovskite photodetector structure schematic diagram of the invention.
Fig. 2 is the structural representation of medium of the invention/medium/metal electrode.
Specific embodiment
With reference to specific embodiment, the present invention is described further, it should be appreciated that each functional layer in each embodiment
As long as and preparation method thereof do not conflict and can be replaced mutually.
Embodiment one
A kind of perovskite photodetector based on medium/medium/metal electrode and preparation method thereof, device architecture such as Fig. 1 institutes
Show, from bottom to top including transparent substrates, medium/medium/metal electrode, perovskite photosensitive layer, charge transport layer, reflecting electrode institute
Composition；As described in Figure 2, including front medium layer, metal level and rear dielectric layer are constituted described medium/medium/metal electrode.Specifically
Ground, device architecture is Glass/MoO3/Au/ PEDOT:PSS / CH3NH3PbClxI3-x/PCBM/Ag.The preparation of device is successively
Comprise the following steps：(1) transparent substrates cleaning：Rotary glass as transparent substrates, transparent substrates successively using acetone, water,
Glass cleaner is cleaned, cleaning finish after in isopropanol, deionized water, each ultrasonically treated 15 minutes of ethanol, used after being disposed
High pure nitrogen is dried up, and is then placed within uviol lamp, is irradiated 20 minutes；(2) medium/medium/metal electrode is prepared：A, selection
Be fitted into glass transparent substrate in vacuum coating equipment as front medium layer by MoO3, when vacuum is less than 5 × 10-4Afterwards, it is saturating in glass
Method on bright substrate by hot evaporation deposits 10-50 nm MoO3As preceding electrode layer；B, in MoO3Continue heat on front medium layer
Evaporation 5-50 nm Au are used as metal level；C deposits one layer of PEDOT on Au metal levels by the method for rotary coating:PSS conducts
Dielectric layer, wherein rotating speed 2000-5000 rpm, rotational time 30-60s afterwards；(3) perovskite photosensitive layer is prepared:It is molten using a step
Liquid method deposits perovskite photosensitive layer on medium/medium/metal electrode；Selection dimethylformamide is used as solvent, configuration mole
Than 1：3 PbCl2And CH3NH3The perovskite precursor solution of I, before rotary coating perovskite on medium/medium/metal electrode
Liquid solution is driven, rotating speed 1500-4000 rpm, rotational time 20-50 s anneals 60 minutes in 100 DEG C of heating plates and completes perovskite
The preparation of photosensitive layer；(4) charge transport layer is prepared：Selection PCBM configures the PCBM of certain mass fraction as charge transport layer
Chlorobenzene solution, fully dissolving after, by its rotary coating on perovskite photosensitive layer, rotating speed 1000-3000 rpm；70 DEG C of annealing
10 minutes；(5) reflecting electrode is prepared：Above-mentioned substrate is fitted into vacuum coating equipment, when vacuum is less than 5 × 10-4After Pa, sink
100 nm Ag reflecting electrodes of product, complete the preparation of device.
Embodiment two
A kind of perovskite photodetector based on medium/medium/metal electrode and preparation method thereof, specifically, device architecture
It is Glass/TiO2/Ag/TiO2/ CH3NH3PbI3/spiro-OMeTAD/Au.The preparation of device is comprised the following steps successively：
(1) transparent substrates cleaning：Medium/medium/metal electrode is prepared with embodiment one (2)：A, selection TiO2As preceding medium
Layer, configures the TiCl of certain mass fraction4Ethanol solution, this solution rotating is coated on glass, rotating speed 2000-4500
Rpm, anneals 60 minutes in 120 DEG C of heating plates, the preparation of medium before completing；B, transparent substrates are fitted into vacuum coating equipment, surely
Reciprocal of duty cycle is less than 5 × 10-4Afterwards, in TiO2Hot evaporation 5-50 nm Ag are used as metal level on front medium layer；C, on Ag metal levels lead to
Cross technique for atomic layer deposition and grow one layer of TiO of densification2Layer is used as rear dielectric layer；(3) perovskite photosensitive layer is prepared:Use two steps
Solwution method deposits perovskite photosensitive layer on medium/medium/metal electrode；Used as solvent, configuration rubs selection dimethylformamide
Your fraction is the PbI of 1M2Solution, selection isopropanol is the CH of the mg/ml of solvent configuration quality fraction 503NH3I solution, medium/
First rotary coating PbI on medium/metal electrode2Solution, rotating speed 1500-3000 rpm, rotational time 20-40 s, 100 DEG C of heating
Dried 3 minutes on plate, then in PbI2Upper rotary coating CH3NH3I solution, rotating speed 2000-3500 rpm, rotational time 25-45
S, being then placed over being annealed in 95 DEG C of heating plates completes the preparation of perovskite photosensitive layer for 120 minutes；(4) charge transport layer is prepared：
Selection spiro-OMeTAD configures the chlorobenzene solution of the spiro-OMeTAD of certain mass fraction, fully as charge transport layer
After dissolving, by its rotary coating on perovskite photosensitive layer, rotating speed 1000-3000 rpm, rotational time 20-40 s；(5) make
Standby reflecting electrode：Above-mentioned substrate is fitted into vacuum coating equipment, when vacuum is less than 5 × 10-4After Pa, 80 nm Au are anti-for deposition
Radio pole, completes the preparation of device.
Embodiment three
Device architecture is Glass/WoO3/Ag/TiO2/CH3NH3PbI3/P3HT/Au。
Example IV
Device architecture is Glass/ZnO/Ag/ZnO/CH3NH3PbI3/CBP/Al。
Embodiment five
Device architecture is Glass/ZnO/Au/PEDOT:PSS/CH3NH3PbClxI3-x/C60/Ag。
Claims (5)
1. a kind of perovskite photodetector based on medium/medium/metal electrode, it is characterised in that wrap successively from bottom to top
Include transparent substrates, medium/medium/metal electrode, perovskite photosensitive layer, charge transport layer, reflecting electrode to be constituted, described Jie
Matter/medium/metal electrode be three-decker, including front medium layer and rear dielectric layer and be clipped in two layer medium layer in metal level
Constituted；Its dielectric layer is hole-transporting type MoO3、WoO3、PEDOT:PSS, ZnO or TiO2In transparent conductive medium one
Plant or two kinds, metal level is the one kind in Ag, Al, Au or Cu.
2. a kind of perovskite photodetector based on medium/medium/metal electrode as claimed in claim 1, its feature exists
In described perovskite photosensitive layer is CH3NH3PbX3Perovskite material, wherein X=Cl, Br, I or their mixture.
3. a kind of perovskite photodetector based on medium/medium/metal electrode as claimed in claim 1, its feature exists
In, when the rear dielectric layer in medium/medium/metal electrode is electron transport material, selection hole mobile material NPB, TCTA,
One kind in TAPC, CBP, P3HT, spiro-OMeTAD is used as charge transport layer；After Jie in medium/medium/metal electrode
When matter layer is for hole mobile material, electric transmission class material C is selected60、C70、Bphen、BCP、Alq3, a kind of conduct in PCBM
Charge transport layer.
4. a kind of perovskite photodetector based on medium/medium/metal electrode as claimed in claim 1, its feature exists
In described metallic reflective electrodes are Al, Ag or Au.
5. as claimed in claim 1 a kind of perovskite photodetector and its preparation side based on medium/medium/metal electrode
Method, it is characterised in that the preparation of device is comprised the following steps：
(1) transparent substrates cleaning
Transparent substrates are successively using acetone, water, glass cleaner cleaning, and cleaning is each in isopropanol, deionized water, ethanol after finishing
Ultrasonically treated 15 minutes, dried up with high pure nitrogen after being disposed, be then placed within uviol lamp, irradiated 20 minutes；
(2) medium/medium/metal electrode is prepared
First, one layer of front medium layer is deposited by methods such as hot evaporation, rotary coating, magnetron sputtering, ALD on a transparent substrate,
Front medium layer thickness 10-50 nm；
Then, layer of metal layer, metal layer thickness 5- are grown by the method for hot evaporation or magnetron sputtering on front medium layer
50 nm；
Finally, dielectric layer after one layer of regrowth, rear thickness of dielectric layers 10-50 nm on the metal layer；
(3) perovskite photosensitive layer is prepared
One layer of perovskite photosensitive layer, perovskite light are prepared on medium/medium/metal electrode using solwution method or coevaporation method
The thickness of photosensitive layer is in 100-1000nm；
(4) charge transport layer is prepared
A layer charge transport layer is deposited on perovskite photosensitive layer using thermal evaporation deposition or spin coating method；Charge transport layer is thick
Degree is in 10-50nm；
(5) reflecting electrode is prepared
By the method deposition of reflective electrode of hot evaporation on charge transport layer, the preparation of device is completed.
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| CN111525036A (en) * | 2020-04-17 | 2020-08-11 | 华东师范大学 | Self-driven perovskite photoelectric detector and preparation method thereof |
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