CN107316943B - Wide wavestrip photodetector and preparation method thereof based on bustamentite caesium carbonamidine film - Google Patents

Wide wavestrip photodetector and preparation method thereof based on bustamentite caesium carbonamidine film Download PDF

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CN107316943B
CN107316943B CN201710575821.1A CN201710575821A CN107316943B CN 107316943 B CN107316943 B CN 107316943B CN 201710575821 A CN201710575821 A CN 201710575821A CN 107316943 B CN107316943 B CN 107316943B
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film
pbi
photodetector
insulating glass
wavestrip
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CN107316943A (en
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梁凤霞
王九镇
梁林
童小伟
王迪
罗林保
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Hefei University of Technology
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/451—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a metal-semiconductor-metal [m-s-m] structure
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E10/549—Organic PV cells

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Abstract

The invention discloses the wide wavestrip photodetectors and preparation method thereof based on bustamentite caesium carbonamidine film, are that the upper surface of insulating glass is provided with FA0.85Cs0.15PbI3Film, in FA0.85Cs0.15PbI3A pair of gold film electrode with it in Ohmic contact is provided on film.Photodetector of the invention utilizes FA0.85Cs0.15PbI3The characteristics of film large specific surface area, the electron mobility of its superelevation is made full use of simultaneously, so that response device speed is ultrafast, and light absorpting ability has opened up new prospect in the application of photodetector for perovskite material by force, to ultraviolet light to visible-range induction is sensitive, electromagnetism interference is strong.

Description

Wide wavestrip photodetector and preparation method thereof based on bustamentite caesium carbonamidine film
Technical field
The invention belongs to semiconductor photo detector fields, and in particular to a kind of wide wavestrip based on bustamentite caesium carbonamidine film Utra-Fast Photodetector and preparation method thereof.
Background technique
With the rapid development of modern science and technology, photodetector (PD) is in scientific research, production, military affairs, optical research etc. Field suffers from very great meaning.Since width absorbs photodetector, in the fields such as industry and science and technology, there is extensive Purposes, so up to the present many people find a kind of extensive wide wavestrip light absorption by combining different functional material Material, can be from ultraviolet to the photodetector of visible region to produce.Different sensitive detection parts have different application necks Domain, such as ultraviolet region detector can be used for ultraviolet light guidance, detection cancer cell, observe the luminescence phenomenon of earthquake and the inspection of water quality It surveys, and visible-light detector part is mainly used for radionetric survey and detection, industry automatic control etc..In addition in spaceship, fire Monitoring, explosive detection etc. photodetector also have important application value.Optical detector be using the light of different wave length as Energy excitation semiconductor generates a large amount of electron hole pairs, so that luminous energy is converted to electric energy, and has one kind of instrument detection quantization Function element, therefore need to research and develop novel optical detector material in industrial circle and scientific domain and make it in different spectrum Having spectral response in range just has very important meaning.At present in ultraviolet region, the preparation of most of photodetector is Based on the inorganic material such as silicon substrate or silicon carbide, since these inorganic device manufacturing conditions are excessively harsh such as at high cost, manufacture work Skill is relative complex, leads to that expensive, weight is big, and application band narrow range is difficult to the photoelectric conversion of wide scope.If necessary Develop a kind of light-detecting device for having response in the ultraviolet spectral region to visible light, it is necessary to by preparing multilayer device It realizes, this just further increases the manufacturing cost of device and the complexity of technique.
As performance of the people to material proposes more requirements, a variety of materials are continuously emerged, two in indulging more materials Dimension nano film material possesses immeasurable potentiality.Due to the characteristics of nano-material surface energy is high, large specific surface area, and work as material When material enters nanometer range, significant change occurs for the relevant electricity of material, magnetics, optical property, can with two-dimension nano materials To produce photodetector that is cheap, haveing excellent performance, the research interest of more and more people is attracted.Organic inorganic hybridization Perovskite can be used as the raw material of two-dimension nano materials, in addition compared with inorganic light-detecting device, organic inorganic hybridization perovskite Light-detecting device is with material selection range is wide, manufacturing cost is low, simple solution processing preparation process and flexibility etc. can be used Advantage.What makes more sense is that organic inorganic hybridization perovskite optical detector can also realize high-quantum efficiency, high sensitivity, height Response speed, wide spectrum response range and low cost.Thus, organic inorganic hybridization perovskite optical detector can be used as wide spectrum and ring The new research direction answered.
Summary of the invention
The invention discloses the wide wavestrip photodetectors and preparation method thereof based on bustamentite caesium carbonamidine film, it is intended to sufficiently Utilize FA0.85Cs0.15PbI3The mobility of film superelevation and extensive absorbing wavelength, provide that a kind of preparation process is simple, light absorption The wide wavestrip Utra-Fast Photodetector that ability is strong, and anti-electromagnetic interference capability sensitive to visible photoinduction is strong.
The present invention is to realize goal of the invention, is adopted the following technical scheme that
The present invention is based on the wide wavestrip photodetectors of bustamentite caesium carbonamidine film, are provided in the upper surface of insulating glass FA0.85Cs0.15PbI3Film, in the FA0.85Cs0.15PbI3A pair of and FA is provided on film0.85Cs0.15PbI3Film In the gold film electrode of Ohmic contact.
It is specific: the FA0.85Cs0.15PbI3Film is n-type perovskite material.The FA0.85Cs0.15PbI3Film is By PbI2, CsI and carbonamidine hydriodate FAI be dissolved in the precursor solution formed in DMSO and DMF, in the upper surface of insulating glass Spin-coating film obtains.The FA0.85Cs0.15PbI3The thickness of film is between 150~200nm.
Preferably, the thickness of the gold film electrode is in 50~100nm.
The preparation method of above-mentioned width wavestrip photodetector, is to carry out as follows:
(1) insulating glass is successively used to acetone, alcohol and deionized water ultrasonic cleaning, then through being dried with nitrogen；It is then placed in In plasma cleaner, plasma cleaning is carried out using oxygen as working gas, it is spare；
(2) PbI of 0.461g is sequentially added in vial2, 0.0389g CsI and 0.145g carbonamidine hydriodate FAI, is then added the DMF of the DMSO and 0.8mL of 0.2mL, and finally sealed and at 70oC heating stirring 1 hour obtains presoma Solution；
(3) insulating glass after cleaning is placed on centrifuge, the precursor solution of 0.1mL is dripped in insulating glass Then upper surface is centrifuged 1 minute with 3000 revs/min of revolving speed, and when centrifugation starts 10 seconds in the upper surface of insulating glass The ethyl acetate of 0.5mL is added dropwise again as anti-solvent to improve quality of forming film；Print is placed into 140oC on hot plate after centrifugation Annealing 20 minutes, then cools to room temperature, i.e., forms FA in the upper surface of insulating glass0.85Cs0.15PbI3Film；
(4) in the FA0.85Cs0.15PbI3Then mask film covering version on film is existed by electron beam plated film FA0.85Cs0.15PbI3Gold thin film is deposited on film, forms a pair of and FA0.85Cs0.15PbI3Film is thin in the gold of Ohmic contact Membrane electrode completes the preparation of wide wavestrip Utra-Fast Photodetector.
Photodetector of the invention is based on FA0.85Cs0.15PbI3/ Au is formed by Ohmic contact, concrete operating principle As follows: device is with FA0.85Cs0.15PbI3Thin-film material is core, utilizes FA0.85Cs0.15PbI3Band gap itself determine to light Absorption peak (i.e. Vis), to present entire device to the absorbability of visible light.Compared to general body material, FA0.85Cs0.15PbI3Thin-film material has bigger specific surface area, and absorption incident light that can be bigger forms the photoelectricity of enhancing Stream, and then enhance the photoelectric characteristic of device.The present invention is not to achieve the purpose that improve device performance using simple strategy To prepare the pretty good approach of photoelectric device.
Compared with the prior art, the beneficial effects of the present invention are embodied in:
1, photodetector of the invention utilizes FA0.85Cs0.15PbI3The characteristics of film large specific surface area, while sufficiently benefit With the electron mobility of its superelevation so that response device speed is ultrafast, and light absorpting ability it is strong, to ultraviolet light to visible-range Incude that sensitive, electromagnetism interference is strong, has opened up new prospect in the application of photodetector for perovskite material.
2, the FA that the present invention is synthesized using one-step synthesis0.85Cs0.15PbI3Film, it is marshalling, uniform in size, make it With bigger specific surface area, and because its surfacing can be good at contacting with gold electrode, device is further improved Energy.
Detailed description of the invention
Fig. 1 is that the present invention is based on FA0.85Cs0.15PbI3The structural schematic diagram of the wide wavestrip Utra-Fast Photodetector of film, Figure label: 1 is insulating glass；2 be FA0.85Cs0.15PbI3Film；3 be gold film electrode.
Fig. 2 is 1 gained FA of the embodiment of the present invention0.85Cs0.15PbI3The SEM of film schemes, wherein (a) is FA0.85Cs0.15PbI3 Side SEM figure, (b) of film are FA0.85Cs0.15PbI3The surface SEM of film schemes.
Fig. 3 is the absorption spectrum curve of 1 gained photodetector sample of the embodiment of the present invention.
Fig. 4 is that current-voltage relation characteristic of the 1 gained photodetector sample of the embodiment of the present invention under dark condition is bent (a) and visible light (white light) and (254 nanometers) of ultraviolet light irradiation under current-voltage relation characteristic curve (b).
Fig. 5 be 1 gained photodetector sample of the embodiment of the present invention respectively under dark condition and wavelength 650nm light Current-vs-time characteristic under the irradiation of source.
Specific embodiment
Below by embodiment, the present invention is described in detail, and following embodiments are under the premise of the technical scheme of the present invention Implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention be not limited to it is following Embodiment.
Experimental method used in following embodiments is conventional method unless otherwise specified.
Agents useful for same, material etc. unless otherwise specified, commercially obtain in the following example.
Embodiment 1
Referring to Fig. 1, the photodetector of the present embodiment is that the upper surface of insulating glass 1 is provided with FA0.85Cs0.15PbI3 Film 2, in FA0.85Cs0.15PbI3A pair of and FA is provided on film 20.85Cs0.15PbI3Film is electric in the gold thin film of Ohmic contact Pole 3.
Wherein: insulating glass used is the common quartz glass of thickness 1.2mm；FA0.85Cs0.15PbI3Film is n-type calcium Titanium ore material；Gold film electrode is obtained by electron beam evaporation plating, thickness 50nm.
The photodetector of the present embodiment is to be prepared as follows:
(1) insulating glass is successively used to acetone, alcohol and deionized water ultrasonic cleaning, then through being dried with nitrogen；It is then placed in It in the vacuum cavity of plasma cleaner, is vacuumized, when vacuum degree is extracted into 1x10-1When Pa, being filled with oxygen is transferred to air pressure 5Pa, by start button to sample clean ten minutes, so that the film in later period can be supported on glass.
(2) PbI of 0.461g is sequentially added in vial2, 0.0389g CsI and 0.145g FAI, be then added The DMF of the DMSO and 0.8mL of 0.2mL, finally sealed and at 70oC heating stirring 1 hour obtain flaxen precursor solution；
(3) insulating glass after cleaning is placed on centrifuge, the precursor solution of 0.1mL is dripped in insulating glass Then upper surface is centrifuged 1 minute with 3000 revs/min of revolving speed, and when centrifugation starts 10 seconds in the upper surface of insulating glass The ethyl acetate of 0.5mL is added dropwise again as anti-solvent to improve quality of forming film；Print is placed into 140oC on hot plate after centrifugation Annealing 20 minutes, then cools to room temperature, i.e., forms FA in the upper surface of insulating glass0.85Cs0.15PbI3Film；
Fig. 2 is FA obtained by the present embodiment0.85Cs0.15PbI3The SEM of film schemes, wherein (a) is FA0.85Cs0.15PbI3Film Side SEM figure, (b) be FA0.85Cs0.15PbI3The surface SEM of film schemes, it can be seen that and it is film marshalling, uniform in size, And surfacing.
(4) in FA0.85Cs0.15PbI3Mask film covering version on film, then by electron beam plated film in FA0.85Cs0.15PbI3 Gold thin film is deposited on film, forms a pair of and FA0.85Cs0.15PbI3Film is in gold film electrode (two electrodes of Ohmic contact Between have 18 microns of channel), that is, complete the preparation of wide wavestrip Utra-Fast Photodetector.
Convenient for test, to put silver paste on gold film electrode as extraction electrode.
The absorption spectrum curve of photodetector sample obtained by the present embodiment as shown in figure 3, under dark condition (a) and The current-voltage relation characteristic curve of (b) is as shown in figure 4, electric current-under visible light (white light) and (254 nanometers) of ultraviolet light irradiations Time relationship characteristic curve is as shown in Figure 5.
As can be seen from Figure 3 the peak in the spectral response of sample is located approximately at 400nm, and spectral response ends in At 800nm, FA has been corresponded to0.85Cs0.15PbI3Forbidden bandwidth (1.51eV)；Therefore the detector of the present embodiment is visible really Light photodetector, and there is quite high response speed.From fig. 4, it can be seen that sample is under 3V bias, dark current only has 1.94×10-11A, electric current has reached 3.31 × 10 under ultraviolet lighting-9A, and under visible light photograph electric current reached 3.18 × 10-8A.From fig. 5, it can be seen that the response speed of device is ultrafast, rise time 117ns, fall time 148ns.
The above is only exemplary embodiment of the present invention, are not intended to limit the invention, all in spirit and original of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within then.

Claims (6)

1. the wide wavestrip photodetector based on bustamentite caesium carbonamidine film, it is characterised in that: the photodetector is to insulate The upper surface of glass is provided with FA0.85Cs0.15PbI3Film, in the FA0.85Cs0.15PbI3Be provided on film it is a pair of with it is described FA0.85Cs0.15PbI3Film is in the gold film electrode of Ohmic contact.
2. width wavestrip photodetector according to claim 1, it is characterised in that: the FA0.85Cs0.15PbI3Film is N-type perovskite material.
3. width wavestrip photodetector according to claim 1, it is characterised in that: the FA0.85Cs0.15PbI3Film is By PbI2, CsI and carbonamidine hydriodate FAI be dissolved in the precursor solution formed in DMSO and DMF, in the upper surface of insulating glass Spin-coating film obtains.
4. width wavestrip photodetector according to claim 1 or 3, it is characterised in that: the FA0.85Cs0.15PbI3Film Thickness between 150~200nm.
5. width wavestrip photodetector according to claim 1, it is characterised in that: the thickness of the gold film electrode is 50 ~100nm.
6. the preparation method of wide wavestrip photodetector described in a kind of any one of Claims 1 to 5, it is characterized in that by such as Lower step carries out:
(1) insulating glass is successively used to acetone, alcohol and deionized water ultrasonic cleaning, then through being dried with nitrogen；Be then placed in etc. from In sub- cleaning machine, plasma cleaning is carried out using oxygen as working gas, it is spare；
(2) PbI of 0.461g is sequentially added in vial2, 0.0389g CsI and 0.145g carbonamidine hydriodate FAI, so Afterwards be added 0.2mL DMSO and 0.8mL DMF, finally sealed and 70 DEG C heating stirring 1 hour, obtain precursor solution；
(3) insulating glass after cleaning is placed on centrifuge, the precursor solution of 0.1mL is dripped in the upper table of insulating glass Then face is centrifuged 1 minute with 3000 revs/min of revolving speed, and drip again when centrifugation starts 10 seconds in the upper surface of insulating glass Add the ethyl acetate of 0.5mL as anti-solvent to improve quality of forming film；Print is placed into 140 DEG C of annealing on hot plate after centrifugation It 20 minutes, then cools to room temperature, i.e., forms FA in the upper surface of insulating glass0.85Cs0.15PbI3Film；
(4) in the FA0.85Cs0.15PbI3Mask film covering version on film, then by electron beam plated film in FA0.85Cs0.15PbI3 Gold thin film is deposited on film, forms a pair of and FA0.85Cs0.15PbI3Film is in the gold film electrode of Ohmic contact, that is, is completed The preparation of wide wavestrip photodetector.
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