CN109888049A - Inorganic perovskite thick-film composite material semiconductor devices and preparation method thereof - Google Patents
Inorganic perovskite thick-film composite material semiconductor devices and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of inorganic perovskite thick-film composite material semiconductor devices and preparation method thereof, can reach and be able to carry out continuous growth, prepare the X-ray detector of big, better crystallinity degree the perovskite polycrystalline thick film of size, and structure is transparent glass/CsPbBr3Perovskite polycrystalline thick film/Au electrode full-inorganic perovskite planar-type semiconductor detector.The detector thickness that we make is thicker, on-off ratio with higher, faster response speed and excellent water oxygen stability.The preparation method step of the semiconductor detector is simple, at low cost, and process low temperature is controllable, and prepared CsPbBr3Material moisture-proof excellent heat resistance, and the method is applied into large-scale commercial production, there is significant industrialization promotion value.
Description
Technical field
The present invention relates to a kind of semiconductor detector device and its preparation processes, multiple more particularly to a kind of perovskite thick film
Close semiconductor detector device and preparation method thereof, the material fabrication process technical field applied to semiconductor detector.
Background technique
Semiconductor detector has very important in military or civil fields such as biologic medical sensing, high energy particle detections
Effect.In recent years, halide perovskite material becomes the hot research material of scientific research circle due to its excellent photoelectric properties,
The good characteristics such as the band gap, high carrier mobility, the carrier lifetime of length and the low defect that properly and easily adjust, make calcium titanium
Mine semiconductor detector becomes a kind of completely new, low cost, low temperature preparation novel semi-conductor detector.Currently used perovskite
Material is mainly organic inorganic hybridization perovskite (for example, CH3NH3PbX3), photoelectric properties are excellent, but water oxygen stability and
Thermal stability is very poor, not radiation hardness and synthesis difficulty is higher, is unfavorable for large area preparation, so preparation size is big, better crystallinity degree
And stable full-inorganic perovskite crystal thick film is likely to become a kind of great prospect applied to high energy particle detection direction
New material.
Compared with organic inorganic hybridization halide perovskite material, full-inorganic halide perovskite material has superior resistance to
Hydrothermal stability.Due to full-inorganic lead halide perovskite CsPbX3(X=I, Br, Cl) also has suitable band gap, it is sufficient to match in excellence or beauty
The high-quantum efficiency of organic inorganic hybridization perovskite, high sensitivity, raw material needed for synthesis more easily obtain and cheap, and
It can be prepared by low temperature solution polycondensation, so it is a kind of substitution of very potential organic inorganic hybridization perovskite material
Product.In recent years, CsPbBr3Crystalline material is successfully obtained by low temperature solution polycondensation, its nano-crystal film, polycrystal film mostly by
For visible-light detector, for photoelectric device photoswitc ratio up to 10^6, the response time is microsecond rank.Also it has been reported that and passes through
The method of inversion crystallization grows CsPbBr3Monocrystal material, μ τ value is up to 2*10-4cm2/V。
For business high energy particle detection application, the thick film or monocrystal material of larger size are needed.Pass through inversion at present
Grow CsPbBr3Monocrystalline still can not extensive, large scale growth, do not have repeatability.CsPbBr3The film of material can not expire
The physical requirement of sufficient high energy particle detection.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
Inorganic perovskite thick-film composite material semiconductor devices and preparation method thereof grows CsPbBr3The preparation method of polycrystalline thick film, reaches
To continuous growth is able to carry out, the X-ray detector of big, better crystallinity degree the perovskite polycrystalline thick film of size, structure are prepared
For transparent glass/CsPbBr3Perovskite polycrystalline thick film/Au electrode full-inorganic perovskite planar-type semiconductor detector.This hair
The preparation method step of bright semiconductor detector is simple, at low cost, and process low temperature is controllable, and prepared CsPbBr3Material is resistance to
Wet excellent heat resistance, and the method is applied into large-scale commercial production.The detector thickness that the present invention makes is thicker, have compared with
High brightness electric current ratio and excellent water oxygen stability.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of inorganic perovskite thick-film composite material semiconductor devices, mainly by transparent glass, perovskite light-absorption layer, metal
Electrode composition, structure are by transparent glass/CsPbBr3Perovskite polycrystalline thick film/Au electrode composition composite construction, it is described
Bright glass is as substrate, as full-inorganic perovskite planar-type semiconductor material for detector, CsPbBr3Perovskite polycrystalline thick film is made
For electron hole transfer function layer, CsPbBr3Perovskite polycrystalline thick film with a thickness of 10~200 μm, Au electrode with a thickness of 70-
90nm。
Above-mentioned CsPbBr3The thickness of perovskite polycrystalline thick film is preferably 100~200 μm.
Above-mentioned perovskite light-absorption layer preferably passes through single step hot spray process and is prepared.
Above-mentioned metal electrode is preferably made of Au point electrode.
Above-mentioned inorganic perovskite thick film multiple device is preferably as X-ray thick film detector device.
A kind of preparation method of the inorganic perovskite thick-film composite material semiconductor devices of the present invention, includes the following steps:
A. substrate pre-treatment:
Glass substrate is successively put into acetone, ethyl alcohol, is cleaned by ultrasonic respectively at least 15 minutes in deionized water, is then used
It is dried with nitrogen glass substrate, then with UV ozone environmental treatment at least 5 minutes, obtains clean glass substrate, it is spare；
B. reactant system solution is prepared:
The CsPbBr of perovskite light-absorption layer is prepared according to target3The stoichiometric ratio of material composition, successively weigh CsBr and
PbBr2Powder is put into reagent bottle is mixed together, is then respectively adding the mixed solvent of DMSO and DMF, and mixture is molten
Liquid is placed on magnetic stirring apparatus and is stirred overnight, and after being then allowed to stand, top clear solution is taken to be filtered, and it is molten to complete reactant system
Liquid process for preparation obtains reactant system solution；
C. full-inorganic perovskite CsPbBr is prepared3Polycrystalline thick film:
Clean glass substrate obtained in the step a is put on warm table and is heated, using hot spray process,
Spray gun is vertically arranged in set height position above glass substrate, the pressure of spray gun gas outlet is adjusted, starts to spray, it will be described
The reactant system solution even application prepared in step b on a glass substrate, completes a spraying process；Then according to setting
Adjacent spraying process time interval, repeat spraying process step, obtain CsPbBr3Thick film layers；Then by the thickness after spraying
Film is placed in anneal station and is made annealing treatment, and obtains CsPbBr of the thickness at 10~200 μm3Perovskite polycrystalline thick film；
D. gold electrode is prepared:
Using evaporation vapor deposition method in the step c CsPbBr3Prepare gold electrode on perovskite polycrystalline thick film, into
Before row evaporation, electrode mask version is first placed in CsPbBr3On perovskite polycrystalline thick film, control evaporation rate is not less than 0.1nm/
S, the thickness of the gold electrode of vapor deposition are finally 70-90nm, to obtain with transparent glass/CsPbBr3Perovskite polycrystalline thick film/
The inorganic perovskite thick-film composite material semiconductor devices of Au electrode composite construction.
It, when carrying out preparation solution, is successively weighed in the step b as currently preferred technical solution
The PbBr of the CsBr and 3.5508g of 2.0589g2Powder is put into reagent bottle together as raw material, is then respectively adding 22.5mL
DMSO and 22.5mL DMF as solvent, the mixture solution of raw material and solvent is placed on magnetic stirring apparatus and is being not higher than
At 80 DEG C, it is stirred overnight with the speed not less than 800r/min, after being then allowed to stand at least 4 hours, takes top clear solution
It is filtered, completes reactant system solution process for preparation, obtain reactant system solution.
As currently preferred technical solution, in the step c, full-inorganic perovskite CsPbBr is being prepared3Polycrystalline
When thick film, clean glass substrate obtained in the step a is put on warm table and is heated, and is heated to being not less than
150 DEG C, using hot spray process, spray gun is vertically arranged in the altitude range of 10~15cm above glass substrate, adjusts spray gun outlet
The pressure of mouth starts spraying and is no more than 15 seconds to 0.1MPa is not less than, the reactant system solution that will be prepared in the step b
Even application on a glass substrate, completes a spraying process；Then not according to the time interval of the adjacent spraying process of setting
It lower than 1 minute, repeats this spraying process step and is sprayed again, repeating this spraying process step 10~200 time, obtaining
CsPbBr3Thick film layers；Then the thick film after spraying is placed in the anneal station not less than 150 DEG C and is made annealing treatment at least 30 points
Clock obtains CsPbBr of the thickness at 10~200 μm3Perovskite polycrystalline thick film.
As currently preferred technical solution, in the step c, full-inorganic perovskite CsPbBr is being prepared3Polycrystalline
When thick film, it is not less than 1 minute according to the time interval of the adjacent spraying process of setting, repeats spraying process step and sprayed again
It applies, is repeating this spraying process step 100~200 time, obtaining CsPbBr3Thick film layers；Then the thick film after spraying is placed on not
It is made annealing treatment in anneal station lower than 150 DEG C at least 30 minutes, obtains CsPbBr of the thickness at 100~200 μm3Perovskite
Polycrystalline thick film.
As currently preferred technical solution, in the step d, using the method for evaporation vapor deposition, in the step c
Middle CsPbBr3Gold electrode is prepared on perovskite polycrystalline thick film, before being evaporated, is first covered interpolation electrode mask plate or point electrode
Template is placed in CsPbBr3On perovskite polycrystalline thick film, it is then evaporated vapor deposition, obtains patterned metal electrode layer.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. the method for the present invention uses hot spray process, full-inorganic perovskite CsPbBr is prepared3The semiconductor probe of polycrystalline thick film
Device, preparation process is simple, and experimental raw is at low cost and easy acquisition, and fabrication cycle is short and repeated height, is suitble to large area extensive
Industrialized production；
2. the method for the present invention provides the promotion semiconductor detector performance that one kind is easily realized by changing process
Method；
3. semiconductor detector prepared by the method for the present invention has a provisioning response to high-energy ray, existing very high damp and hot steady
Fixed and excellent photoelectric respone.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the inorganic perovskite thick-film composite material semiconductor devices of the embodiment of the present invention one.
Fig. 2 is the CsPbBr of one method of embodiment of the present invention preparation3The X-ray diffractogram of polycrystalline thick film.
Fig. 3 is the CsPbBr3 polycrystalline thick film of the different-thickness prepared using one~embodiment tripartite's method of the embodiment of the present invention
I-V characteristic curve comparison figure of the assembled semiconductor detector of sensitive detection parts under the laser illumination of 405nm.
Fig. 4 is the CsPbBr3 polycrystalline thick film detector part group prepared using one~embodiment tripartite's method of the embodiment of the present invention
I-V characteristic curve comparison figure of the semiconductor detector installed under the X-ray ray of different voltages.
Specific embodiment
Above scheme is described further below in conjunction with specific implementation example, the preferred embodiment of the present invention is described in detail such as
Under:
Embodiment one:
In the present embodiment, referring to Fig. 1, a kind of inorganic perovskite thick-film composite material semiconductor devices, the transparent glass
The substrate that glass is 2cm*2cm as planar dimension, inorganic perovskite thick-film composite material semiconductor devices is by transparent glass, calcium titanium
Mine light-absorption layer, metal electrode composition, structure are by transparent glass/CsPbBr3Perovskite polycrystalline thick film/Au electrode composition is answered
Structure is closed, as full-inorganic perovskite planar-type semiconductor material for detector, CsPbBr3Perovskite polycrystalline thick film is as electronics sky
Cave transfer function layer, CsPbBr3Perovskite polycrystalline thick film with a thickness of 10 μm, Au electrode with a thickness of 70nm.The perovskite
Light-absorption layer is prepared by single step hot spray process.The metal electrode is made of Au point electrode.The inorganic perovskite is thick
Film multiple device is as X-ray thick film detector device.
In the present embodiment, referring to Fig. 1, a kind of system of the inorganic perovskite thick-film composite material semiconductor devices of the present embodiment
Preparation Method includes the following steps:
A. substrate pre-treatment:
The glass substrate that planar dimension is 2cm*2cm is successively put into acetone, ethyl alcohol, is cleaned by ultrasonic in deionized water respectively
15 minutes, then using being dried with nitrogen glass substrate, then with UV ozone environmental treatment 5 minutes, clean glass substrate is obtained,
It is spare；
B. reactant system solution is prepared:
Successively weigh the PbBr of the CsBr and 3.5508g of 2.0589g2Powder is put into reagent bottle together as raw material, so
It is separately added into the DMF of the DMSO and 22.5mL of 22.5mL afterwards as solvent, the mixture solution of raw material and solvent is placed on magnetic force
On blender at 80 DEG C, it is stirred overnight with the speed of 800r/min, after being then allowed to stand 4 hours, takes top clear solution
It is filtered, completes reactant system solution process for preparation, obtain reactant system solution；
C. full-inorganic perovskite CsPbBr is prepared3Polycrystalline thick film:
Clean glass substrate obtained in the step a is put on warm table and is heated, and is heated to 150
DEG C, using hot spray process, spray gun is vertically arranged in the altitude range of 10~15cm above glass substrate, adjusts spray gun gas outlet
Pressure starts spraying 15 seconds, by the reactant system solution even application prepared in the step b in glass lined to 0.1MPa
On bottom, a spraying process is completed；Then according to time interval 1 minute of the adjacent spraying process of setting, it is spray coated to repeat this
Journey step is sprayed again, is being repeated this spraying process step 10 time, is being obtained CsPbBr3Thick film layers；It then will be after spraying
Thick film, which is placed in 150 DEG C of anneal station, carries out annealing 30 minutes, obtains CsPbBr of the thickness at 10 μm3Perovskite polycrystalline is thick
Film；
D. gold electrode is prepared:
Using evaporation vapor deposition method in the step c CsPbBr3Prepare gold electrode on perovskite polycrystalline thick film, into
Before row evaporation, point electrode mask is first placed in CsPbBr3On perovskite polycrystalline thick film, control evaporation rate is 0.1nm/s,
The thickness of the gold electrode of vapor deposition is finally 70nm, to obtain with transparent glass/CsPbBr3Perovskite polycrystalline thick film/Au electricity
The inorganic perovskite thick-film composite material semiconductor devices of pole composite construction.
Experimental test and analysis:
To made from the present embodiment have transparent glass/CsPbBr3Perovskite polycrystalline thick film/Au electrode composite construction nothing
Machine perovskite thick-film composite material semiconductor devices carries out properties of sample detection.The CsPbBr that the present embodiment is obtained3Thick film into
The analysis of row XRD characterization, and there is transparent glass/CsPbBr to assembled3Perovskite polycrystalline thick film/Au electrode composite construction
I-V characteristic curve under inorganic perovskite thick-film composite material semiconductor device test I-V characteristic curve, X-ray irradiation.These are surveyed
Examination analysis result is listed in respectively in 2~Fig. 4 of attached drawing.As can be seen from Figure 2 be CsPbBr3 thick film XRD material phase analysis, be located at 11 °,
22 °, 31 ° and 45.5 ° respectively correspond CsPbBr3(101), (121), the diffraction maximum of (202) and (242) crystal face, and not having
There are other miscellaneous peaks, it was demonstrated that the quality of perovskite thick film is fine, along (101) and (121) crystal face preferential growth.As can be seen from Figure 3
Be CsPbBr3The photoelectric properties of thick devices, brightness electric current is than up to 102.As can be known from Fig. 4 be CsPbBr3Thick-film device
Photoelectric properties of the part under X-ray irradiation, its brightness electric current ratio has 10 under X-ray ray at lower power, shows that this is
A kind of inorganic perovskite material for the Detector for High Energy Particles being potential.
Embodiment two:
The present embodiment is basically the same as the first embodiment, and is particular in that:
In the present embodiment, a kind of inorganic perovskite thick-film composite material semiconductor devices, the transparent glass is as flat
Substrate of the face having a size of 2cm*2cm, inorganic perovskite thick-film composite material semiconductor devices is by transparent glass, perovskite extinction
Layer, metal electrode composition, structure are by transparent glass/CsPbBr3Perovskite polycrystalline thick film/Au electrode composition composite junction
Structure, as full-inorganic perovskite planar-type semiconductor material for detector, CsPbBr3Perovskite polycrystalline thick film is passed as electron hole
Transmission function layer, CsPbBr3Perovskite polycrystalline thick film with a thickness of 100 μm, Au electrode with a thickness of 80nm.The perovskite extinction
Layer is prepared by single step hot spray process.The metal electrode is made of Au point electrode.The inorganic perovskite thick film is multiple
Clutch part is as X-ray thick film detector device.
In the present embodiment, referring to Fig. 1, a kind of system of the inorganic perovskite thick-film composite material semiconductor devices of the present embodiment
Preparation Method includes the following steps:
A. substrate pre-treatment:
The glass substrate that planar dimension is 2cm*2cm is successively put into acetone, ethyl alcohol, is cleaned by ultrasonic in deionized water respectively
15 minutes, then using being dried with nitrogen glass substrate, then with UV ozone environmental treatment 5 minutes, clean glass substrate is obtained,
It is spare；
B. reactant system solution is prepared:
Successively weigh the PbBr of the CsBr and 3.5508g of 2.0589g2Powder is put into reagent bottle together as raw material, so
It is separately added into the DMF of the DMSO and 22.5mL of 22.5mL afterwards as solvent, the mixture solution of raw material and solvent is placed on magnetic force
On blender at 80 DEG C, it is stirred overnight with the speed of 800r/min, after being then allowed to stand 4 hours, takes top clear solution
It is filtered, completes reactant system solution process for preparation, obtain reactant system solution；
C. full-inorganic perovskite CsPbBr is prepared3Polycrystalline thick film:
Clean glass substrate obtained in the step a is put on warm table and is heated, and is heated to 150
DEG C, using hot spray process, spray gun is vertically arranged in the altitude range of 10~15cm above glass substrate, adjusts spray gun gas outlet
Pressure starts spraying 15 seconds, by the reactant system solution even application prepared in the step b in glass lined to 0.1MPa
On bottom, a spraying process is completed；Then according to time interval 1 minute of the adjacent spraying process of setting, it is spray coated to repeat this
Journey step is sprayed again, is being repeated this spraying process step 100 time, is being obtained CsPbBr3Thick film layers；It then will be after spraying
Thick film, which is placed in 150 DEG C of anneal station, carries out annealing 30 minutes, obtains CsPbBr of the thickness at 100 μm3Perovskite polycrystalline
Thick film；
D. gold electrode is prepared:
Using evaporation vapor deposition method in the step c CsPbBr3Prepare gold electrode on perovskite polycrystalline thick film, into
Before row evaporation, point electrode mask is first placed in CsPbBr3On perovskite polycrystalline thick film, control evaporation rate is 0.1nm/s,
The thickness of the gold electrode of vapor deposition is finally 80nm, to obtain with transparent glass/CsPbBr3Perovskite polycrystalline thick film/Au electricity
The inorganic perovskite thick-film composite material semiconductor devices of pole composite construction.
Experimental test and analysis:
To made from the present embodiment have transparent glass/CsPbBr3Perovskite polycrystalline thick film/Au electrode composite construction nothing
Machine perovskite thick-film composite material semiconductor devices carries out properties of sample detection.The CsPbBr that the present embodiment is obtained3Thick film into
The analysis of row XRD characterization, and there is transparent glass/CsPbBr to assembled3Perovskite polycrystalline thick film/Au electrode composite construction
Inorganic perovskite thick-film composite material semiconductor device tests I-V characteristic curve.These Measurement results be listed in respectively attached drawing 3~
In Fig. 4.As can be seen from Figure 3 be CsPbBr3 thick devices photoelectric properties, brightness electric current than up to 103, photoelectric current compares
10 times are increased again with the photoelectricity of the CsPbBr3 thick devices of 10 μ m thicks.As can be known from Fig. 4 be CsPbBr3 thick devices
Photoelectric properties under X-ray irradiation, its brightness electric current ratio has 10 under X-ray ray at lower power, and photoelectric current exists
Becoming larger and increasing with X-ray power, shows that this is a kind of inorganic perovskite material of Detector for High Energy Particles being potential
Material.
Embodiment three:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of inorganic perovskite thick-film composite material semiconductor devices, the transparent glass is as flat
Substrate of the face having a size of 2cm*2cm, inorganic perovskite thick-film composite material semiconductor devices is by transparent glass, perovskite extinction
Layer, metal electrode composition, structure are by transparent glass/CsPbBr3Perovskite polycrystalline thick film/Au electrode composition composite junction
Structure, as full-inorganic perovskite planar-type semiconductor material for detector, CsPbBr3Perovskite polycrystalline thick film is passed as electron hole
Transmission function layer, CsPbBr3Perovskite polycrystalline thick film with a thickness of 200 μm, Au electrode with a thickness of 90nm.The perovskite extinction
Layer is prepared by single step hot spray process.The metal electrode is made of Au point electrode.The inorganic perovskite thick film is multiple
Clutch part is as X-ray thick film detector device.
In the present embodiment, referring to Fig. 1, a kind of system of the inorganic perovskite thick-film composite material semiconductor devices of the present embodiment
Preparation Method includes the following steps:
A. substrate pre-treatment:
The glass substrate that planar dimension is 2cm*2cm is successively put into acetone, ethyl alcohol, is cleaned by ultrasonic in deionized water respectively
15 minutes, then using being dried with nitrogen glass substrate, then with UV ozone environmental treatment 5 minutes, clean glass substrate is obtained,
It is spare；
B. reactant system solution is prepared:
Successively weigh the PbBr of the CsBr and 3.5508g of 2.0589g2Powder is put into reagent bottle together as raw material, so
It is separately added into the DMF of the DMSO and 22.5mL of 22.5mL afterwards as solvent, the mixture solution of raw material and solvent is placed on magnetic force
On blender at 80 DEG C, it is stirred overnight with the speed of 800r/min, after being then allowed to stand 4 hours, takes top clear solution
It is filtered, completes reactant system solution process for preparation, obtain reactant system solution；
C. full-inorganic perovskite CsPbBr is prepared3Polycrystalline thick film:
Clean glass substrate obtained in the step a is put on warm table and is heated, and is heated to 150
DEG C, using hot spray process, spray gun is vertically arranged in the altitude range of 10~15cm above glass substrate, adjusts spray gun gas outlet
Pressure starts spraying 15 seconds, by the reactant system solution even application prepared in the step b in glass lined to 0.1MPa
On bottom, a spraying process is completed；Then according to time interval 1 minute of the adjacent spraying process of setting, it is spray coated to repeat this
Journey step is sprayed again, is being repeated this spraying process step 200 time, is being obtained CsPbBr3Thick film layers；It then will be after spraying
Thick film, which is placed in 150 DEG C of anneal station, carries out annealing 30 minutes, obtains CsPbBr of the thickness at 200 μm3Perovskite polycrystalline
Thick film；
D. gold electrode is prepared:
Using evaporation vapor deposition method in the step c CsPbBr3Prepare gold electrode on perovskite polycrystalline thick film, into
Before row evaporation, point electrode mask is first placed in CsPbBr3On perovskite polycrystalline thick film, control evaporation rate is 0.1nm/s,
The thickness of the gold electrode of vapor deposition is finally 90nm, to obtain with transparent glass/CsPbBr3Perovskite polycrystalline thick film/Au electricity
The inorganic perovskite thick-film composite material semiconductor devices of pole composite construction.
Experimental test and analysis:
To made from the present embodiment have transparent glass/CsPbBr3Perovskite polycrystalline thick film/Au electrode composite construction nothing
Machine perovskite thick-film composite material semiconductor devices carries out properties of sample detection.The CsPbBr that the present embodiment is obtained3Thick film into
The analysis of row XRD characterization, and there is transparent glass/CsPbBr to assembled3Perovskite polycrystalline thick film/Au electrode composite construction
Inorganic perovskite thick-film composite material semiconductor device tests I-V characteristic curve.These Measurement results be listed in respectively attached drawing 3~
In Fig. 4.As can be seen from Figure 3 be CsPbBr3 thick devices photoelectric properties, brightness electric current than up to 103, photoelectric current compares
10 times are increased with the photoelectricity of the CsPbBr3 thick devices of 10 μ m thicks, but photoelectric current, also already close to saturation, thickness is to light
The generation of electric current also has a certain impact, by data it is concluded that 100 μm -200 μm of thickness is optimal.It can from Fig. 4
What is known is photoelectric properties of the CsPbBr3 thick devices under X-ray irradiation, its brightness under X-ray ray at lower power
Electric current ratio has 10, and photoelectric current shows that this is a kind of high energy particle being potential in becoming larger and increasing with X-ray power
The inorganic perovskite material of detector.
To sum up described in embodiment, inorganic perovskite thick-film composite material semiconductor devices is by transparent glass, perovskite extinction
Layer, metal electrode composition, wherein perovskite light-absorption layer is prepared by single step hot spray process, is that one kind has electron hole biography
The material of transmission function.Metal electrode is made of Au point electrode.The above embodiment of the present invention is to pass through thermal jet on transparent glass
Coating prepares full-inorganic perovskite CsPbBr3Light-absorption layer obtains high-performance on its basis by thermal evaporation deposition electrode material
The inorganic perovskite CsPbBr of plane3Semiconductor detector, carrying out assembling has different-thickness full-inorganic perovskite CsPbBr3
The X-ray detector of polycrystalline thick film.Above-described embodiment grows CsPbBr3The preparation method of polycrystalline thick film, reaches the company of being able to carry out
Continuous growth, prepares the X-ray detector of big, better crystallinity degree the perovskite polycrystalline thick film of size, structure be transparent glass/
CsPbBr3Perovskite polycrystalline thick film/Au electrode full-inorganic perovskite planar-type semiconductor detector.Furthermore the present invention is using steaming
The method of hair vapor deposition prepares interpolation gold electrode, and interpolation electrode mask version is placed on CsPbBr3 thick film before evaporation, can be also deposited
The thickness of gold electrode be finally 70-90nm；It can get X-ray thick film detector as a result,.The detector of above-described embodiment production
Thickness is thicker, on-off ratio with higher, faster response speed and excellent water oxygen stability.The semiconductor detector
Preparation method step is simple, at low cost, and process low temperature is controllable, and prepared CsPbBr3Material moisture-proof excellent heat resistance, and will
The method applies to large-scale commercial production, has significant industrialization promotion value.
Combination attached drawing of the embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, substitution, combination or the simplification made, should be equivalent substitute mode, as long as meeting goal of the invention of the invention,
Without departing from the technical principle and invention of the inorganic perovskite thick-film composite material semiconductor devices of the present invention and preparation method thereof
Design, belongs to protection scope of the present invention.
Claims (10)
1. a kind of inorganic perovskite thick-film composite material semiconductor devices, the transparent glass is as substrate, it is characterised in that: nothing
Machine perovskite thick-film composite material semiconductor devices is mainly made of transparent glass, perovskite light-absorption layer, metal electrode, structure
For by transparent glass/CsPbBr3Perovskite polycrystalline thick film/Au electrode composition composite construction, as full-inorganic perovskite plane
Type semiconductor detector material, CsPbBr3Perovskite polycrystalline thick film is as electron hole transfer function layer, CsPbBr3Perovskite is more
Brilliant thick film with a thickness of 10~200 μm, Au electrode with a thickness of 70-90nm.
2. inorganic perovskite thick-film composite material semiconductor devices according to claim 1, it is characterised in that: CsPbBr3Calcium titanium
Mine polycrystalline thick film with a thickness of 100~200 μm.
3. inorganic perovskite thick-film composite material semiconductor devices according to claim 1, it is characterised in that: the perovskite
Light-absorption layer is prepared by single step hot spray process.
4. inorganic perovskite thick-film composite material semiconductor devices according to claim 1, it is characterised in that: the metal electricity
Pole is made of Au point electrode.
5. inorganic perovskite thick-film composite material semiconductor devices according to claim 1, it is characterised in that: the inorganic calcium
Titanium ore thick film multiple device is as X-ray thick film detector device.
6. the preparation method of inorganic perovskite thick-film composite material semiconductor devices described in a kind of claim 1, which is characterized in that
Include the following steps:
A. substrate pre-treatment:
Glass substrate is successively put into acetone, ethyl alcohol, is cleaned by ultrasonic at least 15 minutes in deionized water respectively, then uses nitrogen
Glass substrate is dried up, then with UV ozone environmental treatment at least 5 minutes, obtains clean glass substrate, it is spare；
B. reactant system solution is prepared:
The CsPbBr of perovskite light-absorption layer is prepared according to target3The stoichiometric ratio of material composition successively weighs CsBr and PbBr2
Powder is put into reagent bottle is mixed together, is then respectively adding the mixed solvent of DMSO and DMF, mixture solution is put
It is stirred overnight on magnetic stirring apparatus, after being then allowed to stand, top clear solution is taken to be filtered, completed reactant system solution and match
Process processed obtains reactant system solution；
C. full-inorganic perovskite CsPbBr is prepared3Polycrystalline thick film:
Clean glass substrate obtained in the step a is put on warm table and is heated, using hot spray process, will be sprayed
Rifle is vertically arranged in set height position above glass substrate, adjusts the pressure of spray gun gas outlet, starts to spray, will be in the step
The reactant system solution even application prepared in b on a glass substrate, completes a spraying process；Then according to the phase of setting
The time interval of adjacent spraying process repeats spraying process step, obtains CsPbBr3Thick film layers；Then the thick film after spraying is put
It is made annealing treatment in anneal station, obtains CsPbBr of the thickness at 10~200 μm3Perovskite polycrystalline thick film；
D. gold electrode is prepared:
Using evaporation vapor deposition method in the step c CsPbBr3Gold electrode is prepared on perovskite polycrystalline thick film, is being steamed
Before hair, electrode mask version is first placed in CsPbBr3On perovskite polycrystalline thick film, control evaporation rate is not less than 0.1nm/s, steams
The thickness of the gold electrode of plating is finally 70-90nm, to obtain with transparent glass/CsPbBr3Perovskite polycrystalline thick film/Au electricity
The inorganic perovskite thick-film composite material semiconductor devices of pole composite construction.
7. the preparation method of inorganic perovskite thick-film composite material semiconductor devices according to claim 6, it is characterised in that:
In the step b, when carrying out preparation solution, the PbBr of the CsBr and 3.5508g of 2.0589g are successively weighed2Powder conduct
Raw material is put into reagent bottle together, is then respectively adding the DMF of the DMSO and 22.5mL of 22.5mL as solvent, by raw material with
The mixture solution of solvent is placed on magnetic stirring apparatus at not higher than 80 DEG C, is stirred with the speed not less than 800r/min
Overnight, after being then allowed to stand at least 4 hours, top clear solution is taken to be filtered, completes reactant system solution process for preparation, obtains
To reactant system solution.
8. the preparation method of inorganic perovskite thick-film composite material semiconductor devices according to claim 6, it is characterised in that:
In the step c, full-inorganic perovskite CsPbBr is being prepared3It, will be clean obtained in the step a when polycrystalline thick film
Glass substrate is put on warm table and is heated, and is heated to, using hot spray process, spray gun being vertically arranged in not less than 150 DEG C
The altitude range of 10~15cm above glass substrate adjusts the pressure of spray gun gas outlet to 0.1MPa is not less than, starts spraying not
More than 15 seconds, on a glass substrate by the reactant system solution even application prepared in the step b, primary spraying is completed
Process；Then it is not less than 1 minute according to the time interval of the adjacent spraying process of setting, repeats this spraying process step and carry out again
Secondary spraying is repeating this spraying process step 10~200 time, is obtaining CsPbBr3Thick film layers；Then the thick film after spraying is placed on
It is made annealing treatment in anneal station not less than 150 DEG C at least 30 minutes, obtains CsPbBr of the thickness at 10~200 μm3Calcium titanium
Mine polycrystalline thick film.
9. the preparation method of inorganic perovskite thick-film composite material semiconductor devices according to claim 8, it is characterised in that:
In the step c, full-inorganic perovskite CsPbBr is being prepared3When polycrystalline thick film, according to setting adjacent spraying process when
Between interval be not less than 1 minute, repeat spraying process step sprayed again, repeatedly this spraying process step 100~200
It is secondary, obtain CsPbBr3Thick film layers；Then the thick film after spraying is placed in the anneal station not less than 150 DEG C and is made annealing treatment
At least 30 minutes, obtain CsPbBr of the thickness at 100~200 μm3Perovskite polycrystalline thick film.
10. the preparation method of inorganic perovskite thick-film composite material semiconductor devices, feature exist according to claim 6
In: in the step d, using the method for evaporation vapor deposition, the CsPbBr in the step c3It is prepared on perovskite polycrystalline thick film
Interpolation electrode mask plate or point electrode mask are first placed in CsPbBr before being evaporated by gold electrode3Perovskite polycrystalline thick film
On, it is then evaporated vapor deposition, obtains patterned metal electrode layer.
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