CN108677169B - A kind of preparation facilities of organic ammonium metal halide film and preparation and characterizing method - Google Patents
A kind of preparation facilities of organic ammonium metal halide film and preparation and characterizing method Download PDFInfo
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Abstract
The present invention provides a kind of preparation facilities of organic ammonium metal halide film and preparation and characterizing methods, belong to perovskite material field, by combining out-phase reaction kinetics of diffusion and balance thermodynamics of reactions double control in the substrate with metal halide using illumination assistant chemical vapor deposition method, the ABX for the high quality being made of longitudinal perforative big crystal grain has successfully been prepared3Type perovskite thin film, and further phenetic analysis has been carried out by characterization methods such as current-voltage (J-V) curves under atomic force microscope, scanning electron microscope and simulated solar irradiation.Compared with the existing technology, preparation facilities disclosed by the invention and preparation method have be swift in response, be easy to operate, control is accurate, repeatability is high, can the remarkable advantages such as large area preparation, film quality height.
Description
Technical field
The invention belongs to perovskite material fields, in particular to a kind of preparation of organic ammonium metal halide film
Device and preparation and characterizing method.
Background technique
What this part provided is only background information relevant to the disclosure, is not necessarily the prior art.
Develop clean photovoltaic technology and has become a kind of important channel for solving energy crisis and environmental problem.However,
Due to high cost and complicated preparation process, the photovoltaic technology of mainstream, such as crystalline silicon, CuInGaSe2(CIGS) and CdTe
Solar battery still faces huge challenge.In recent years, the height of organic-inorganic halide perovskite solar battery (PSCs)
Photoelectric conversion efficiency (PCE), low cost make it endure concern to the fullest extent with easy technology of preparing.The most classic light absorbing layer of PSCs is answered
It is traditional AMX3Calcium titanium ore bed, crystal structure are the shared MX of apex angle6Octahedron, wherein A are CH3NH3(MA)、CHN2H4
(FA) perhaps Cs M be Pb or Sn, X represent halide ion I, Br and Cl.AMX3 perovskite has several advantages, such as high
The absorption coefficient of light, direct band gap is adjusted and long carrier diffusion distance, due to above-mentioned advantage, so far, the PCE of PSCs
23% is had been over, this presents good application prospect.
There are the means for much preparing perovskite device, such as solwution method, thermal evaporation deposition, vacuum flashing method, original so far
Sublayer sedimentation, scraper for coating method, spray coating method and silk screen print method etc..Most important means are solwution methods, it can be prepared
Efficient PSCs, and cost is not high.However, solvent, which leaves the too fast crystallization process after film and frequently results in, coarse has hole
The film in hole.By contrast, thermal evaporation deposition can prepare smooth pin-free high-quality thin film.However, due to its preparation cost
Higher and high instrument cost leads to its large-scale application relatively difficult to achieve.So developing, one kind is novel to be commercialized
The technology of preparing of PSCs is necessary.2013, a kind of new preparation means gas phase assisted solution method (VASP) was by Yang etc.
The advantages of human hair is bright, and this method combines vapor phase method and solwution method, in simple terms, PbI2Film is first spin-coated on substrate
On, then reacted in a closed space with MAI gas again.This achievement is using gas-solid reaction in situ as preparation PSCs
Means.It develops to 2018, the PCE of the PSCs of such methods preparation is thus lifted to 18% or more.The characteristics of its device is benefit
PSCs is prepared with the high temperature MAI steam in glassware, however, the reaction of VASP method is slower, is easy to cause reaction insufficient.
A kind of faster tubular type CVD technology of reaction is also successfully applied to preparation PSCs, and this method is very easy, repeated height, can
It prepares high quality perovskite thin film (referring to Fig. 1).In general, tubular type CVD uses quartz ampoule, MAI steam is carried using nitrogen
Prepare PSCs.Then, a variety of CVD technologies have been also applied in preparation PSCs, for example, by tube furnace, flowmeter, quartz ampoule with
And heating source composition tube-type chemical vapour deposition process (ITCVD) (referring to fig. 2) in situ, use the tube furnace one in dual temperature area
Walk tube-type chemical vapour deposition process (referring to Fig. 3), using the spraying auxiliary of the hot substrate control laminar flow to suspend on the glass substrate
CVD, be vapor-deposited (HPCVD, ginseng by quartz ampoule, the halide physical chemistry that continuous heating temperature is driven and vacuum evacuation device is constituted
See Fig. 4) etc. various titles be previously used.Currently, CVD method can be divided into two step tube-type chemical vapour deposition processes according to step
(two step CVD) and step tube-type chemical vapour deposition process (a step CVD), wherein two step CVD method, according to specific device feature,
The referred to as titles such as mixed chemical vapour deposition process (HCVD), low-pressure chemical vapor deposition (LPCVD) and ITCVD；Wherein, HCVD
It was proposed in 2014 by Qi seminar, has shown high flexibility.After this or Qi seminar reports HCVD (ginseng
See Fig. 5) method of the synthesis based on FA perovskite, the method provides the approach of preparation in quantity PSCs and high duplication,
Device is mainly made of the quartz ampoule that can lead to carrier gas, another two steps HCVD method is proposed by Zheng et al., uses one end
Quartz ampoule into gas other end discharge gas forms preparation facilities (referring to Fig. 6), and the PSCs of vacuum aided method preparation is most
High PCE reaches 18.9%, and its preparation condition is under normal pressure and between humidity 30-65%.LPCVD is used in PSCs
In, this method has apparent cost advantage, low-energy-consumption and the advantage reacted faster.2015, Shen et al.
LPCVD is used to prepare perovskite, device has quartz ampoule and a graphite canoe to guarantee the uniformity of MAI steam
(referring to Fig. 7), this covering device has the advantages of higher yield and large area can be prepared compared with technology before, with upper tube
In formula, MAI, which needs to spread, gets to forerunner's film surface over long distances, this will significantly influence the reproducibility of PSCs, to understand
The MAI technology close with precursor film is suggested by certainly this problem, referred to as ITCVD (Luo et al.).Li et al. people improves this
Tubular type CVD has been changed to two hot plates of longitudinal arrangement, referred to as near space vapor transport method (CSVT) by one technique, essence
It is also a kind of CVD technology.The invention proposes a kind of similar devices, but MAI is sprayed on upper substrate, and precursor film is placed on lower base
On plate.A kind of different CVD technology is directly reacted from the above MAI and lead iodide to be developed in 2017 by Yan et al..They are sharp
Be prepared for stable PSCs with low partial pressure MA gas, principle be controlled by two pressure reducing valves MA gases be passed through cylindrical vessel come
Prepare device (referring to Fig. 8), be swift in response, preparation process it is simple so that its PCE reaches 18.9%.Qi et al.,
By preparing mixed system perovskite (referring to Fig. 9) in conjunction with cation exchange and HCVD method, the PCE promotion of PSCs is arrived
18% or more；Another method is a step CVD method, its main feature is that preparing PSCs by primary gas phase reaction.Fan et al. report
This one step tube-type chemical gas phase of tube furnace for using dual temperature area sinks method, and the PCE of the PSCs of preparation is 11.1%, and
And this similarly suitable large area preparation of method, the method for one step CVD of another kind is spraying auxiliary AACVD method, its main feature is that logical
Cross carrier gas transfer forerunner's aerosol solution preparation PSCs.Later, Lewis et al. is for the first time in preparation MAPbBr3The process of perovskite
In used this method, AACVD has been attract attention, because it is a kind of CVD technology of dual-pressure, it makes
With being sprayed for precursor molecule, then by inert gas carrier, if argon gas is to substrate surface translocation aerosol, but still not greatly
Area prepares longitudinal perforative crystal grain.
In conclusion following technology drawback exists in the prior art: 1, cannot be effective by thermodynamics of reactions and dynamics
There is the shortcomings that reaction is not exclusively when preparing high thickness thin film and/or crystal grain cannot longitudinally run through in the reaction process for controlling film；
2, diffusion velocity of the halogen in metal halide film is slow, to hinder longitudinal formation for running through crystal grain；3, cannot
Enough prepare large area, efficient organic-inorganic halide perovskite solar battery film material (PSCs).
Summary of the invention
The present invention provides a kind of preparation method, it is therefore an objective to one of above-mentioned problems of the prior art are at least solved, it should
Purpose is achieved through the following technical solutions:
A kind of preparation method of organic ammonium metal halide film has using described in the preparation of light auxiliary chemical vapor deposition method
Machine ammonium metal halide film, the preparation method include:
Step 1 passes through vacuum evaporation or polar non-solute additive method preparation knot in the substrate of precleaning
The low metal halide film of brilliant degree；
Substrate with metal halide film sample is placed in device chamber by step 2 together with organic ammonium halide powder
In body, and described device cavity is evacuated to 100~1000Pa；
Step 3 is carried out in two steps, first the progress first step, in the case where metal halide film-substrate does not heat,
By organic ammonium halide powder intensity of illumination be 2~4mW/cm2Illumination condition under be heated to distilling, then carry out second
Step, is heated to 100~160 DEG C for the metal halide film and the organic ammonium halide powder jointly and reacts；
Step 4 stops heating described device cavity after reaction, takes out the organic ammonium metal halide being successfully prepared
Object film.
Optionally, the metal halide is in lead chloride, lead bromide, lead iodide, selenium chloride, selenium bromide and iodate selenium
One or more of combinations.
Optionally, the organic ammonium halide is chloromethane ammonium, chloroethene ammonium, chlorine formamidine salt, chlorine dimethylammonium, bromine first ammonium, bromine second
The combination of one or more of ammonium, bromine formamidine salt, bromine dimethylammonium, iodine first ammonium, iodine second ammonium, iodine formamidine salt and iodine dimethylammonium.
Further, different according to substrate and film thickness in the step 3, the reaction time is 5~40 minutes or 20~
50 minutes.
Further, the second step in the step 3, according to substrate difference, reaction condition is to have illumination or unglazed
According to.
Further, the organic ammonium metal halide film product being prepared in the step 4 includes CH3NH3PbI3。
Device used by a kind of preparation method such as above-mentioned organic ammonium metal halide film, described device include one
The device cavity of cylindrical shape, the intracorporal bottom of device chamber, which is provided with down, to be heated the substrate, under the upper surface that heats the substrate be provided with
Pbl2Film substrate, Pbl2The upper surface of film substrate is placed in place organic bittern compound, the organic salt halide
It is transparent heat the substrate and under heat the substrate between, the top open part of device cavity is equipped with lid, upper transparent in device cavity
Heating the substrate is light accessory channel between the lid, and clear quartz window, clear quartz window are provided on the lid
Top be hung with light source, the light beam of light source reaches through clear quartz window and light accessory channel and upper transparent heats the substrate table
Face, and pass through upper transparent heat the substrate and illumination is applied to reactant, it is additionally provided on the side side wall of device cavity to take out
The vacuum passage of vacuumizing.
Optionally, the light source is LED light source system.
A kind of organic ammonium metal halide that the preparation method characterizing above-mentioned organic ammonium metal halide film is prepared
The method of film product, using atomic force microscope or scanning electron microscope to the organic ammonium metal halide film
Particle is analyzed and characterized, further, it is also possible to the electric current according to the organic ammonium metal halide film under simulated solar irradiation
Density vs. voltage (J-V) curvilinear characteristic is characterized and is divided to the incident photon-to-electron conversion efficiency of the organic ammonium metal halide film
Analysis, or use film thickness analytic approach, ultraviolet-visible absorption spectroscopy analytic approach are to the quality of the organic ammonium metal halide film
It is analyzed.
Compared with the existing technology, the present invention achieves significant technical effect:
1, the present invention passes through the reaction process of thermodynamics of reactions and dynamics Controlling film, successfully overcomes and prepares high thickness
Film reaction not exclusively or crystal grain cannot longitudinally through the shortcomings that and it is traditional by lead iodide films react before preannealing, without control
The solar energy film material PSCs of method processed preparation is compared, this method have be swift in response, be easy to operate, control is accurate, can weigh
The advantages that renaturation is high.
2, the method that first passage of the present invention is introduced into illumination successfully promotes the halide ion in halide in metal halogen
Longitudinal diffusion in compound film makes longitudinal direction be formed into possibility through crystal grain.
3, the present invention can prepare the organic ammonium metal halide film product for running through crystal grain with longitudinal direction of large area, be
Solar battery provides photoelectric conversion material and traditional annealing, the film sun without control method preparation efficiently, inexpensive
Energy material perovskite thin film is compared, and product prepared by the present invention has many advantages, such as large area and uniformity, film quality are high.
Detailed description of the invention
By reading the following detailed description of the preferred embodiment, various other advantages and benefits are common for this field
Technical staff will become clear.The drawings are only for the purpose of illustrating a preferred embodiment, and is not considered as to the present invention
Limitation.And throughout the drawings, the same reference numbers will be used to refer to the same parts.In the accompanying drawings:
Fig. 1 is the schematic device that tube-type chemical vapour deposition process (CVD) device prepares PSCs in the prior art；
Fig. 2 is the schematic device that tube-type chemical vapour deposition process (ITCVD) in situ prepares PSCs in the prior art；
Fig. 3 is the schematic device that a step tube-type chemical vapour deposition process (CVD) prepares PSCs in the prior art；
Fig. 4 is the schematic device that halide physical chemistry vapor deposition process (HPCVD) prepares PSCs in the prior art；
Fig. 5 is the schematic device that inert carrier gas assisted deposition system CVD method prepares PSCs in the prior art；
Fig. 6 is the schematic device that hot-air assistant chemical vapor deposition prepares PSCs in the prior art；
Fig. 7 is the schematic device for preparing PSCs using in-situ chemical vapor deposition CVD method in the prior art；
Fig. 8 is the schematic device for preparing PSCs using methylamine steam in the prior art；
Fig. 9 is the schematic device for combining CVD and base exchange method to prepare PSCs in the prior art；
Figure 10 is to prepare organic ammonium metal halide using light auxiliary chemical vapor deposition method provided by the embodiment of the present invention
The schematic device of object film；
Figure 11 is provided by the embodiment of the present invention to atomic force microscope (AFM) table for preparing product and being analyzed and characterized
Sign figure；
Figure 12 is provided by the embodiment of the present invention to the scanning electron microscope (SEM) for preparing product and being analyzed and characterized
Phenogram；
Figure 13 is provided by the embodiment of the present invention to preparing that product is analyzed and characterized in solar battery
Photo and device in kind Current density-voltage (J-V) curve graph under simulated solar irradiation.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, below in conjunction with attached drawing and specifically
Embodiment, explanation is described in detail to the application.Although it should be pointed out that showing showing for the disclosure in attached drawing
Example property embodiment, it being understood, however, that may be realized in various forms the disclosure without should be by embodiments set forth herein
It is limited.It is to be able to thoroughly understand the disclosure on the contrary, providing these embodiments, and can be by the model of the disclosure
It encloses and is fully disclosed to those skilled in the art.
In order to solve following problems existing in the prior art: cannot effectively be controlled by thermodynamics of reactions and dynamics thin
The reaction process of film, when preparing high thickness thin film react not exclusively, crystal grain cannot longitudinally run through, halide ion is in metal halide
Longitudinal diffusion speed in film is slow, hinders longitudinal formation for running through crystal grain, cannot prepare large area, efficient organic
Inorganic halides perovskite solar battery (PSCs) thin-film material, the present invention provides a kind of organic ammonium metal halide films
Preparation method, it is as follows using light auxiliary chemical vapor deposition method (PACVD) technique preparation step:
1) crystallinity is prepared by vacuum evaporation or polar non-solute additive method in the substrate of precleaning
Low metal halide film (BX2)；
2) metal halide film (BX will be had2) substrate of film sample sets together with organic ammonium halide (AX) powder
In device cavity, it is evacuated to 100-1000Pa；
3) reaction is divided into two big steps, and according to substrate difference, the reaction time can be 5~40 minutes or 20~50 minutes,
Middle first step BX2Substrate does not heat, only organic ammonium halide (AX) be heated to distillation (100~130 DEG C of temperature of iodine first ammonium,
130~160 DEG C of iodine carbonamidine temperature), the above-mentioned first step has illumination, and intensity of illumination is 2~4mW/cm2, equal quilt both in second step
It is heated to 100~160 DEG C of temperature；According to substrate difference, above-mentioned second step can have illumination or no light；
4) arresting stop cavity heats after reaction, takes out the organic ammonium metal halide film being successfully prepared
(ABX3)。
Specifically, the metal halide (BX2) it can be lead chloride (PbCl2), lead bromide (PbBr2), lead iodide
(PbI2), selenium chloride (SnCl2), selenium bromide (SnBr2) or iodate selenium (SnI2) one of or several combination；It is described
Organic ammonium halide (AX) can be chloromethane ammonium, chloroethene ammonium, chlorine formamidine salt (NH2=CHNH2Cl), chlorine dimethylammonium
(CH3NH2CH3Cl), bromine first ammonium, bromine second ammonium, bromine formamidine salt, bromine dimethylammonium, iodine first ammonium, iodine second ammonium, iodine formamidine salt or iodine dimethylammonium
One of or several combination, for example, the nitrogenous organic salt halide (AX) can be CH3NH3I, that is, iodide
Ammonium (or iodine first ammonium) and CHN2H4The combination of I, that is, iodate carbonamidine (or iodine formamidine salt), above two nitrogenous organic salt halide difference
Belong to the hydriodate of methylamine, carbonamidine.In addition, above-mentioned preparation method be related to prepare product organic ammonium metal halide film
(ABX3) it include common several nitrogenous organic salt metal halide photovoltaic materials, such as CH3NH3PbI3。
Specifically, in the above-mentioned preparation method using low vacuum synthesis organic inorganic hybridization perovskite thin film, by device
Cavity is evacuated to 0.1~1000Pa, by the supreme transparent heater plate surface of nitrogenous organic salt halide (AX) solution spraying, solvent
Volatilization rapidly, using nitrogenous organic salt halide (AX) steam by metal halide (BX under vacuum, illumination condition2) film turn
It is changed to organic ammonium metal halide film (ABX3), this process only needs ten to dozens of minutes, and sustained response, particle is nitrogenous organic
Coalescence in salt halide (AX) steam, until the organic ammonium metal halide film (ABX that reaction generates3) particle stopping length
Greatly, longitudinal perforative crystal grain is generated.
The present embodiment is preparing organic ammonium metal halide film (ABX3) Shi Caiyong isolation air operating method category
In a kind of use in parallel to the Low Pressure Chemical Vapor Deposition of thermal station (LPCVD) technique, when use wet process prepares metal halide
(BX2) film when, do not need using other vacuum evaporation cavitys or vacuum dryer, which is low vacuum level technique, can will
Continuous apparatus is formed with high vacuum vapor deposition cavity after device extension.
In addition, according to substrate difference, the reaction time can choose as 5~40 minutes or 20~50 in the step 3
Minute, the second step in the step 3, according to substrate difference, reaction condition is to have illumination or no light.
A kind of exemplary more detailed preparation process description is shown below:
Firstly, cleaning substrate base: cleaning agent, isopropanol, acetone, each ultrasound 20min of deionized water are used respectively, drying
Argon gas drying, ozone treatment 20 minutes；
Then, by 0.3g PbI2The 80 anhydrous DMI of μ l are dissolved in 0.5mL anhydrous DMF and are added, are heated to 70 DEG C, magnetic force stirs
It mixes 120 minutes, is sufficiently mixed, on the 2.5cm × 2.5cm substrate cleaned up and under the atmosphere of inert gas, 5000rpm
Spin coating PbI2Precursor liquid 30s forms the low PbI of crystallinity2Film；
Then, upper transparent heat the substrate (upper substrate) is heated, by 0.08g CH3NH3Transparent heating base in I spraying
On plate.Again by PbI2Substrate is transferred under device and heats the substrate, and gives PbI2Film about 2mW/cm2White light irradiation；
Then, 700Pa is evacuated to device cavity by vacuum pump, is first heated to 100 DEG C to upper substrate, lower substrate is not
11min, during this, the PbI of yellow are reacted in heating2Film gradually reacts into the CH of brown3NH3PbI3Film；
Then, heating lower substrate is heated to 110 DEG C, reacts 11min in the case where 100 DEG C of upper substrate.Brown
CH3NH3PbI3Film gradually becomes the high black CH of crystallinity3NH3PbI3Film；
Then, 10 DEG C while by upper and lower base plate are increased, reacts 61min, CH with this condition3NH3PbI3It is protected on film appearance
Hold black；
Then, upper substrate heating is closed, reacts 2min, CH with this condition3NH3PbI3Black is still kept on film appearance；
Finally, closing lower substrate heating and vacuum pump, it is filled with argon gas to device, is made and covers on complete, microcosmic by longitudinal direction
Through the CH of crystal grain composition3NH3PbI3Film.
Having metal halide (BX2) substrate on, by it is a kind of exempt from preannealing and illumination auxiliary method, in conjunction with different
Phase reaction kinetics of diffusion and balance thermodynamics of reactions double control, are successfully prepared using illumination assistant chemical vapor deposition method
By the ABX3 type perovskite thin film for the high quality that longitudinal perforative big crystal grain is constituted, the large area device of this film preparation is utilized
The photoelectric conversion efficiency of part (1.8 square centimeters of effective area) reaches 18.8% or more.Relative to traditional annealing, without controlling party
PSCs prepared by method, preparation method provided by the invention, which has, to be swift in response, is easy to operate, controls accurate, repeatability height, is big
The remarkable advantages such as area is uniform, film quality is high.
Referring to Figure 10, in another embodiment, the invention also discloses a kind of such as above-mentioned organic ammonium metal halide
Device used by the preparation method of film, described device include the device cavity 1 an of cylindrical shape, in device cavity 1
Bottom, which is provided with down, heats the substrate 2, under heat the substrate 2 upper surface and be provided with Pbl2Film substrate 3, Pbl2Film substrate 3 it is upper
Side, distance about 6mm have it is upper it is transparent heat the substrate, the organic salt halide 4 be placed in it is transparent heat the substrate 5 lower surface,
It diffuses to after heating and heats the substrate between 2 and 5 up and down, the top open part of device cavity 1 is equipped with lid, in device cavity 1
Upper transparent heat the substrate is light accessory channel 6 between 5 and the lid, and the central position of the lid is provided with suprasil
Window 7, the top of clear quartz window 7 are hung with light source 8, and the light beam of light source 8 penetrates clear quartz window 7 and light accessory channel
6 arrival are above transparent to heat the substrate 5 surfaces, and passes through upper transparent heat the substrate and apply illumination, device cavity 1 to reactant 3
Side side wall on be additionally provided with vacuum passage 9 to vacuum pumping.
In another embodiment, the invention also discloses the preparation sides for characterizing above-mentioned organic ammonium metal halide film
The method for the organic ammonium metal halide film product that method is prepared, further to the organic ammonium metal halide being prepared
Object film carries out performance Parameter analysis:
Characterizing method one:
Referring to Figure 11, using atomic force microscope or scanning electron microscope to the organic ammonium metal halide film
Particle be analyzed and characterized.Atomic force microscope (AFM) phenogram on perovskite thin film surface shows the microscopic particles of film
Uniformly, pin-free, this is very favorable to the performance for improving the electronic device that perovskite is semiconductor material.
Indicator method two:
Referring to Figure 12, according to Current density-voltage (J- of the organic ammonium metal halide film under simulated solar irradiation
V) curvilinear characteristic is characterized and is analyzed to the incident photon-to-electron conversion efficiency of the organic ammonium metal halide film.Perovskite thin film
The scanning electron microscope surface (SEM) and section phenogram, characterization result show that the film particles size being prepared is equal
It is even, longitudinally run through, and the film of this method preparation requires substrate, that is to say, that can be made on any substrate
The perovskite particle of standby any thickness formed by longitudinally running through crystal grain, this is the electronics device of semiconductor material to raising perovskite
The performance of part is very favorable.
Characterizing method three:
Referring to Figure 13, the perovskite solar battery that the preparation method provided according to the present invention is prepared is in simulated solar
Current density-voltage (J-V) curve under light, which is 1.8 square centimeters, and the efficiency of battery has reached 18.8%,
This is very favorable to the performance for improving the electronic device that perovskite is semiconductor material.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, equally replace by the modification that can readily occur in
It changes or improves, should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be wanted with the right
Subject to the protection scope asked.
Claims (8)
1. a kind of preparation method of organic ammonium metal halide film, it is characterised in that: use light auxiliary chemical vapor deposition method
The organic ammonium metal halide film is prepared, step includes:
Step 1 prepares crystallinity by vacuum evaporation or polar non-solute additive method in the substrate of precleaning
Low metal halide film；
Substrate with metal halide film sample is placed in device cavity by step 2 together with organic ammonium halide powder
In, and described device cavity is evacuated to 100~1000Pa；
Step 3 is carried out in two steps, and the progress first step first will have in the case where metal halide film-substrate does not heat
Machine ammonium halide powder is heated to distilling in the case where intensity of illumination is the illumination condition of 2~4mW/cm2, then carries out second step, will
The metal halide film and the organic ammonium halide powder are heated to 100~160 DEG C jointly and are reacted；
Step 4 stops heating described device cavity after reaction, it is thin to take out the organic ammonium metal halide being successfully prepared
Film.
2. a kind of preparation method of organic ammonium metal halide film according to claim 1, it is characterised in that: the gold
Category halide is the combination of one or more of lead chloride, lead bromide, lead iodide, selenium chloride, selenium bromide and iodate selenium.
3. a kind of preparation method of organic ammonium metal halide film according to claim 1, it is characterised in that: described to have
Machine ammonium halide be chloromethane ammonium, chloroethene ammonium, chlorine formamidine salt, chlorine dimethylammonium, bromine first ammonium, bromine second ammonium, bromine formamidine salt, bromine dimethylammonium,
The combination of one or more of iodine first ammonium, iodine second ammonium, iodine formamidine salt and iodine dimethylammonium.
4. a kind of preparation method of organic ammonium metal halide film according to claim 1, it is characterised in that: described
In step 3, according to substrate difference, the reaction time is 5~40 minutes or 20~50 minutes.
5. a kind of preparation method of organic ammonium metal halide film according to claim 1, it is characterised in that: described
Second step in step 3, according to substrate difference, reaction condition is to have illumination or no light.
6. a kind of preparation method of organic ammonium metal halide film according to claim 1, it is characterised in that: the step
The organic ammonium metal halide film product being prepared in rapid four includes CH3NH3PbI3.
7. being filled used by a kind of preparation method such as organic ammonium metal halide film of any of claims 1-6
It sets, it is characterised in that: described device includes the device cavity an of cylindrical shape, and the intracorporal bottom of device chamber is provided with lower heating
Substrate, under the upper surface that heats the substrate be provided with Pbl2 film substrate, the upper of the top of Pbl2 film substrate transparent heats the substrate
To place organic bittern compound, the organic salt halide be placed in it is transparent heat the substrate and under heat the substrate between, dress
The top open part for setting cavity is equipped with lid, and upper transparent heat the substrate between the lid in device cavity is that light auxiliary is logical
Road, the lid are provided with transparent window, and light source is hung with above transparent window, and the light beam of light source penetrates transparent window and light
Accessory channel arrival is above transparent to heat the substrate surface, and passes through upper transparent heat the substrate and apply light to the reactant in substrate
According to being additionally provided with the vacuum passage to vacuum pumping on the side side wall of device cavity.
8. device according to claim 7, it is characterised in that: the light source is light emitting diode, intensity of illumination 2-
4mW/cm2。
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| CN201810475386.XA CN108677169B (en) | 2018-05-17 | 2018-05-17 | A kind of preparation facilities of organic ammonium metal halide film and preparation and characterizing method |
| PCT/CN2018/107637 WO2019218567A1 (en) | 2018-05-17 | 2018-09-26 | Device and method for preparing organic ammonium metal halide film, and representation method |
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| US20220230813A1 (en) * | 2019-06-03 | 2022-07-21 | Mecaroenergy Co., Ltd. | Method for preparing perovskite solar cell absorbing layer by means of chemical vapor deposition |
| CN110349886B (en) * | 2019-06-19 | 2022-02-15 | 江苏大学 | Large-area perovskite solar cell preparation device and preparation method |
| CN110551999B (en) * | 2019-09-26 | 2022-02-08 | 济南大学 | Method for loading iodine on medical titanium alloy equipment |
| CN111682116B (en) * | 2020-05-21 | 2023-07-14 | 常州大学 | Method for preparing perovskite solar cell based on ion exchange |
| WO2021250499A1 (en) * | 2020-06-08 | 2021-12-16 | Okinawa Institute Of Science And Technology School Corporation | Rapid hybrid chemical vapor deposition for perovskite solar modules |
| CN113845896B (en) * | 2021-09-10 | 2023-08-04 | 天津理工大学 | Curved organic ammonium metal halide film, preparation method, solar cell and application |
| CN113948644B (en) * | 2021-10-15 | 2022-08-19 | 华能新能源股份有限公司 | CsPbBr 3 Preparation method of perovskite solar cell |
| CN115295732B (en) * | 2022-09-28 | 2023-02-07 | 无锡极电光能科技有限公司 | Perovskite thin film, preparation method and system thereof, and solar cell |
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