CN106920856B - A kind of electroluminescent and photovoltaic double-function device and preparation method thereof - Google Patents

A kind of electroluminescent and photovoltaic double-function device and preparation method thereof Download PDF

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CN106920856B
CN106920856B CN201710150791.XA CN201710150791A CN106920856B CN 106920856 B CN106920856 B CN 106920856B CN 201710150791 A CN201710150791 A CN 201710150791A CN 106920856 B CN106920856 B CN 106920856B
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晋佳佳
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Jiangsu Di Sheng construction group Co., Ltd
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
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    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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Abstract

The invention discloses a kind of electroluminescent and photovoltaic double-function device and preparation method thereof, it includes transparent conductive substrate, the first decorative layer, perovskite active layer, the second decorative layer and reflecting electrode composition.The double-function device, which has, generates electricity in illumination, the dual function of luminous lighting when being powered.The device architecture and preparation method of the present invention is simple, equipment requirement is low, it is at low cost, be suitable for large-scale industrial production.

Description

A kind of electroluminescent and photovoltaic double-function device and preparation method thereof
Technical field
The present invention relates to a kind of electroluminescent and photovoltaic double-function device and preparation method thereof, belong to semi-conductor photoelectronic device Part technical field.
Background technology
Perovskite solar cell has many advantages, such as that preparation process is simple, at low cost, efficient.Since PARK classes in 2012 Since topic group reports all solid state perovskite solar cell that 500 hours service life or more, efficiency reach 9.7% for the first time, perovskite is too Positive energy battery receives the very big concern of educational circles and industrial circle, quickly grows, goes back quilt《Science》It is chosen as ten big sections in 2013 Learn one of breakthrough.Perovskite solar cell is quickly grown in a few years, the perovskite solar cell reported at present Efficiency has breached 20%.
The research of perovskite solar cell is in the ascendant, and researcher has found that perovskite is simultaneously that one kind is had excellent performance again Luminescent material, have a series of advantage of protrusions：(1) luminous efficiency is high.Photoluminescence efficiency is up to 80% or more； (2) Band gap and spectrum are simply adjustable.Ratio by adjusting different halogen elements can easily realize glow peak from it is visible cover it is close red Outskirt；(3) spectrum colour purity is high, the nm of luminescent spectrum half peak breadth ~ 20；(4) manufacturing cost is cheap, simple for process, can be by molten Liquid method realizes large area production.The number of advantages of perovskite electroluminescent device and its excellent properties shown show it Illumination and huge application prospect in flat display field.
Although verified perovskite is simultaneously a kind of photovoltaic and luminescent material haveing excellent performance, traditional perovskite The device overwhelming majority is simple function device, can only provide the simple function in luminous or photovoltaic, and device integration is poor.Exploitation Take into account luminous and photovoltaic work(double-function device all has important meaning for the research of research perovskite device and commercial application Justice.
Invention content
In order to solve the problems, such as described in background technology, the present invention provides a kind of electroluminescent and photovoltaic double-function device And preparation method thereof.To achieve the goals above, the present invention proposes following technical scheme：
A kind of electroluminescent and photovoltaic double-function device and preparation method thereof, which is characterized in that device architecture is from down to up Include transparent conductive substrate, the first decorative layer, perovskite active layer, the second decorative layer and reflecting electrode composition successively.
Further, the transparent conductive substrate is made a living the glass substrate with ITO, square resistance 10-20 Ω, is penetrated Rate is in 80-90%.
Further, first decorative layer is PEDOT:PSS, PEDOT:The method that PSS is coated by solution rotating It prepares, thickness is in 30-50 nm.
Further, the perovskite active layer is CsPbBr3And CH3NH3PbBr3In one kind, perovskite activity Layer is prepared by the method that solution rotating coats, and thickness is in 50-300 nm.
Further, second decorative layer is one kind in TPBI, Bphen, BCP, and thickness is in 10-50 nm.
Further, the reflecting electrode is one kind in Au, Ag, Al or their alloy, reflecting electrode thickness In 50-200 nm.
Further, device prepare it is further comprising the steps of：
(1) transparent conductive substrate is handled：Transparent conductive substrate is cleaned successively using acetone, glass cleaner, then third It is respectively ultrasonically treated in ketone, deionized water, isopropanol 10 minutes, ultra violet lamp handles 10 minutes for use after being dried up with nitrogen；
It is prepared by (2) first decorative layers：The rotary coating PEDOT in transparent conductive substrate:The aqueous solution of PSS, rotating speed are low Popular 500rpm rotates 5 seconds, high speed 3000-4000rpm, rotates 30-50 seconds；After coating, in 120 degrees Celsius of heating plate Upper heating anneal is handled 20 minutes；
(3) prepared by perovskite photosensitive layer：Organic inorganic hybridization perovskite precursor solution is configured at room temperature, it will be quantitative CsPbBr3Or CH3NH3PbBr3It is dissolved in dimethyl sulfoxide (DMSO) (DMSO), heats and extremely dissolved within 12 hours fully under the conditions of 60 DEG C, Obtain perovskite precursor solution；Using sol evenning machine by precursor solution rotary coating on the first decorative layer；Rotating speed 2000- 3000rpm, rotational time 40-60 seconds；It the moment that perovskite active layer rotary coating finishes, is added dropwise on perovskite active layer The chloroformic solution of 20ml continues rotary coating, rotating speed 2000-3000rpm, rotational time 20-30 seconds；Device is shifted after the completion It anneals 10-30 minutes on to 90 DEG C of heating plates；
It is prepared by (4) second decorative layers：Device is transferred in vacuum coating equipment after the completion, waits for that vacuum degree is less than 5 × 10-4Pa Under conditions of after, by the method for thermal evaporation continue deposit the second decorative layer；
(5) reflecting electrode is prepared：On the second decorative layer by the method for thermal evaporation deposit one layer Al, Ag or Au make For reflecting electrode, perovskite electroluminescent and photovoltaic double-function device are obtained.
Description of the drawings
Fig. 1 is electroluminescent and the photovoltaic double-function device structural schematic diagram of the present invention
Specific implementation mode
Example one：A kind of electroluminescent and photovoltaic double-function device and preparation method thereof, device architecture are illustrated such as Fig. 1 institutes Show, device architecture from down to up successively include transparent conductive substrate, the first decorative layer, perovskite active layer, the second decorative layer and Reflecting electrode forms.Specifically, device architecture ITO（10 Ω of square resistance, transmitance is 85%）/PEDOT:PSS（40 nm）/ CsPbBr3（200 nm）/TPBI （20）/Al （100 nm）, the preparation of device includes step：
The first step, substrate cleaning：
Transparent conductive substrate is cleaned successively using acetone, glass cleaner, each ultrasound in acetone, deionized water, isopropanol Processing 10 minutes, ultra violet lamp is handled 10 minutes after nitrogen drying；
It is prepared by second step, the first decorative layer：
The rotary coating PEDOT in transparent conductive substrate:The aqueous solution of PSS, rotating speed are vulgar 500rpm, are rotated 5 seconds, high Fast 3500rpm rotates 35 seconds；After coating, heating anneal is handled 20 minutes in 120 DEG C of heating plate；
It is prepared by third step, perovskite photosensitive layer：
Inorganic perovskite precursor solution is configured at room temperature, by quantitative CsPbBr3It is dissolved in DMSO, a concentration of 1 M , heat under the conditions of 60 DEG C 12 hours it is abundant to dissolving, obtain CsPbBr3Perovskite precursor solution；Using sol evenning machine by forerunner Liquid solution rotary coating is on the first decorative layer；Rotating speed 2000rpm, rotational time 60 seconds；Perovskite active layer rotary coating is complete Complete moment, the chloroformic solution that 20ml is added dropwise on perovskite active layer continue rotary coating, rotating speed 2000rpm, rotational time 20 seconds；Device is transferred in 90 DEG C of heating plate after the completion and is annealed 10 minutes, extra solvent is removed, it is good to form crystal property Good CsPbBr3Perovskite thin film；
It is prepared by the 4th step, the second decorative layer：
It grows above-mentioned device to be transferred in vacuum coating equipment, after vacuum degree is less than under conditions of 5 × 10-4Pa, passes through heat The method of evaporation continues to deposit the TPBI of 20nm as the second decorative layer；
5th step：Prepare reflecting electrode：
Prepare reflecting electrode：Under vacuum condition of the vacuum degree less than 5 × 10-4, pass through thermal evaporation on the second decorative layer Method deposits the Al of one layer of 100 nm as reflecting electrode, obtains perovskite electroluminescent and photovoltaic double-function device；
6th step, test：
The open-circuit voltage of perovskite electroluminescent and photovoltaic double-function device is measured under the irradiation of AM1.5 analog solar light 1.3V, fill factor 0.40, short circuit current 2.8mA/cm2, energy conversion efficiency 1.45%.Under power-up condition, measures device and open Bright voltage is 3.2V, maximum brightness 2870cd/cm2, luminous peak position is in 527nm or so, half-peak breadth 21nm.Device realizes electricity Photoluminescence and photovoltaic it is difunctional.
Example two：A kind of electroluminescent and photovoltaic double-function device and preparation method thereof, device architecture is from down to up successively It is formed including transparent conductive substrate, the first decorative layer, perovskite active layer, the second decorative layer and reflecting electrode.Specifically, device Structure is ITO（10 Ω of square resistance, transmitance is 85%）/PEDOT:PSS（40 nm）/ CH3NH3PbBr3（300 nm）/ Bphen (20 nm) /Ag （100 nm）, the preparation of device includes step：
The first step, substrate cleaning：With example one；
It is prepared by second step, the first decorative layer：With example one；
It is prepared by third step, perovskite photosensitive layer：
Organic inorganic hybridization perovskite precursor solution is configured at room temperature, by quantitative CH3NH3PbBr3It is molten in DMSO It solves, a concentration of 1.2 M, 12 hours is heated under the conditions of 60 DEG C to dissolving fully, obtains CH3NH3PbBr3Perovskite presoma is molten Liquid；Using sol evenning machine by precursor solution rotary coating on the first decorative layer；Rotating speed 2500rpm, rotational time 50 seconds；Calcium titanium The moment that mine active layer rotary coating finishes, the chloroformic solution that 20ml is added dropwise on perovskite active layer continue rotary coating, turn 2000 turns of speed, rotational time 30 seconds；Device is transferred in 90 DEG C of heating plate after the completion and is annealed 15 minutes, is removed extra molten Agent forms the good CH of crystal property3NH3PbBr3Perovskite thin film；
It is prepared by the 4th step, the second decorative layer：
It grows above-mentioned device to be transferred in vacuum coating equipment, waits for that vacuum degree is less than 5 × 10-4After under conditions of Pa, pass through heat The method of evaporation continues to deposit the Bphen of 20nm as the second decorative layer；
5th step：Prepare reflecting electrode：
Prepare reflecting electrode：Vacuum degree is less than 5 × 10-4Vacuum condition under, pass through thermal evaporation on the second decorative layer Method deposits the Ag of one layer of 100 nm as reflecting electrode, obtains perovskite electroluminescent and photovoltaic double-function device；
6th step, test：
The open-circuit voltage of perovskite electroluminescent and photovoltaic double-function device is measured under the irradiation of AM1.5 analog solar light 1.25V, fill factor 0.32, short circuit current 3.2mA/cm2, energy conversion efficiency 1.28%.Under power-up condition, device is measured It is 3.3V, maximum brightness 3870cd/cm to open bright voltage2, luminous peak position is in 525nm or so, half-peak breadth 20nm.Device is realized Electroluminescent and photovoltaic it is difunctional.

Claims (2)

1. the preparation method of a kind of electroluminescent and photovoltaic double-function device, which is characterized in that electroluminescent and photovoltaic are difunctional The preparation of device includes the following steps：
(1) transparent conductive substrate is handled：Transparent conductive substrate is cleaned successively using acetone, glass cleaner, then acetone, It is respectively ultrasonically treated in deionized water, isopropanol 10 minutes, ultra violet lamp handles 10 minutes for use after being dried up with nitrogen；
It is prepared by (2) first decorative layers：The rotary coating PEDOT in transparent conductive substrate:The aqueous solution of PSS, rotating speed are low speed 500rpm rotates 5 seconds, high speed 3000-4000rpm, rotates 30-50 seconds；After coating, heated in 120 DEG C of heating plate Annealing 20 minutes；
(3) prepared by perovskite photosensitive layer：At room temperature, organic inorganic hybridization perovskite precursor solution is configured；It will be quantitative CsPbBr3 or CH3NH3PbBr3 dissolvings in the dimethyl sulfoxide (DMSO) (DMSO) are heated under the conditions of 60 DEG C 12 hours and are filled to dissolving Point, obtain perovskite precursor solution；Using sol evenning machine by precursor solution rotary coating on the first decorative layer；Rotating speed 2000-3000rpm, rotational time 40-60 seconds；The moment that perovskite active layer rotary coating finishes, on perovskite active layer The chloroformic solution that 20ml is added dropwise continues rotary coating, rotating speed 2000-3000rpm, rotational time 20-30 seconds；After the completion by device It is transferred in 90 DEG C of heating plate and anneals 10-30 minutes；
It is prepared by (4) second decorative layers：Device is transferred in vacuum coating equipment, waits for that vacuum degree is less than 5 × 10-4After Pa, lead to The method for crossing thermal evaporation deposits the second decorative layer；
(5) prepared by reflecting electrode：One layer of Al, Ag or Au are deposited by the method for thermal evaporation on the second decorative layer and are used as reflection Electrode obtains perovskite electroluminescent and photovoltaic double-function device.
2. a kind of electroluminescent and photovoltaic double-function device, feature prepared by preparation method according to claim 1 exist In, device architecture include successively from down to up transparent conductive substrate, the first decorative layer, perovskite active layer, the second decorative layer and Reflecting electrode forms, and the transparent conductive substrate is made a living the glass substrate with ITO, square resistance 10-20 Ω, and transmitance exists 80-90%, first decorative layer are PEDOT:PSS, for thickness in 30-50 nm, the perovskite active layer is CsPbBr3 Or one kind in CH3NH3PbBr3, for thickness in 50-300 nm, second decorative layer is in TPBI, Bphen, BCP One kind, thickness is in 10-50 nm；The reflecting electrode is one kind in Au, Ag, Al or their alloy, and reflecting electrode is thick Degree is in 50-200 nm.
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WO2019009417A1 (en) 2017-07-06 2019-01-10 国立大学法人九州大学 Organic light-emitting element
CN108054287A (en) * 2017-12-01 2018-05-18 南京邮电大学 A kind of efficient organic monolayer light emitting diode and preparation method thereof
CN109841703B (en) * 2019-01-30 2021-06-11 暨南大学 All-inorganic perovskite photoelectric detector and preparation method thereof
CN110010598A (en) * 2019-04-01 2019-07-12 杭州众能光电科技有限公司 A kind of luminous integrated device of perovskite of integration self energizing

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