CN108677169A - 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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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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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, out-phase reaction kinetics of diffusion and balance thermodynamics of reactions double control are combined in the substrate with metal halide by using illumination assistant chemical vapor deposition method, has successfully prepared the ABX for the high quality being made of longitudinal perforative big crystal grain3Type 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 technology
This part provide be only with the relevant background information of the disclosure, be not necessarily the prior art.
Develop clean photovoltaic technology and has become a kind of important channel 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 cell still faces huge challenge.In recent years, the height of organic-inorganic halide perovskite solar cell (PSCs)
Photoelectric conversion efficiency (PCE), low cost make it endure concern to the fullest extent with easy technology of preparing.Light absorbing layer most classical 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) either Cs M be Pb or Sn, X represent halide ion I, Br and Cl.AMX3 perovskites have 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 many means for 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 manufacturing 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 gases again.This achievement is using gas-solid reaction in situ as preparation PSCs
Means.It develops to 2018, the PCE of PSCs prepared by such methods is thus lifted to 18% or more.The characteristics of its device is profit
PSCs is prepared with the high temperature MAI steam in glassware, however, the reaction of VASP methods is slower, it is insufficient to be easy to cause reaction.
A kind of faster tubular type CVD technology of reaction is also successfully applied to prepare PSCs, and this method is very easy, repeated height, can
Prepare 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
It walks tube-type chemical vapour deposition process (referring to Fig. 3), control the spraying auxiliary of laminar flow using the hot substrate 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 extractor 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,
It is referred to as the titles such as mixed chemical vapour deposition process (HCVD), low-pressure chemical vapor deposition (LPCVD) and ITCVD；Wherein, HCVD
It was proposed by Qi seminars in 2014, has shown high flexibility.After this or Qi seminars report HCVD (ginsengs
See Fig. 5) method of the synthesis based on FA perovskites, 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., and one end is used
The quartz ampoule composition preparation facilities (referring to Fig. 6) of gas is discharged into the gas other end, PSCs prepared by vacuum aided method 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 ensure 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 needs to spread gets to forerunner's film surface over long distances, this will significantly influence the reproducibility of PSCs, to understand
The MAI technologies close with precursor film is suggested by certainly this problem, is referred to as ITCVD (Luo et al.).Li et al. people improves this
Tubular type CVD has been made into two hot plates of longitudinal arrangement by one technique, is referred to as near space vapor transport method (CSVT), essence
It is also a kind of CVD technology.The present invention proposes a kind of similar device, 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 by Yan et al. in 2017.They are sharp
Be prepared for stable PSCs with low partial pressure MA gases, principle be by two pressure reducing valves control 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 methods, the PCE promotions of PSCs are 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. is reported
This that the tube furnace one step tube-type chemical gas phase in dual temperature area is used to sink method, the PCE of the PSCs prepared is 11.1%, and
And prepared by this similarly suitable large area of method, the method for one step CVD of another kind is spraying auxiliary AACVD methods, its main feature is that logical
It crosses carrier gas transfer forerunner's aerosol solution and prepares PSCs.Later, Lewis et al. is preparing MAPbBr for the first time3The process of perovskite
In used this method, AACVD to attract attention because it is a kind of CVD technology of dual-pressure, it makes
With the spraying of precursor molecule, then by inert gas carrier, if argon gas is to substrate surface translocation aerosol, but still it is not big
Area prepares longitudinal perforative crystal grain.
In conclusion following technology drawback exists in the prior art：It 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).
Invention content
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 prepares knot in the substrate of precleaning by vacuum evaporation or polar non-solute additive method
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, and carries out the first step first, 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 by the metal halide film and the organic ammonium halide powder and reacts jointly；
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 bottom in device cavity, which is provided with down, to be heated the substrate, under the upper surface that heats the substrate be provided with
Pbl2Film substrate, Pbl2To place organic bittern compound, the organic salt halide is positioned over for the upper surface of film substrate
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
It is light accessory channel to heat the substrate 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 illumination is applied to reactant across upper transparent heat the substrate, it is additionally provided with to take out on the side side wall of device cavity
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 of the above-mentioned organic ammonium metal halide film of characterization 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 electricity conversion 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 technique effect：
1, the present invention successfully overcomes by the reaction process of thermodynamics of reactions and dynamics Controlling film and prepares high thickness
Film reaction not exclusively or crystal grain cannot longitudinally run through the shortcomings that and it is traditional by lead iodide films react before preannealing, without control
Solar energy film material PSCs prepared by method processed 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 cell 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.
Description of the drawings
By reading the detailed description of hereafter preferred embodiment, various other advantages and benefit are common for this field
Technical staff will become clear.Attached drawing only for the purpose of illustrating preferred embodiments, 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 using in-situ chemical vapor deposition CVD method to prepare PSCs in the prior art；
Fig. 8 is the schematic device for utilizing methylamine steam to prepare PSCs 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 prepares organic ammonium metal halide by what the embodiment of the present invention provided using light auxiliary chemical vapor deposition method
The schematic device of object film；
Atomic force microscope (AFM) table being analyzed and characterized to preparing product that Figure 11 is provided by the embodiment of the present invention
Sign figure；
The scanning electron microscope (SEM) being analyzed and characterized to preparing product that Figure 12 is provided by the embodiment of the present invention
Phenogram；
Figure 13 by the embodiment of the present invention provide to preparing that product is analyzed and characterized in solar cell
Photo and device in kind Current density-voltage (J-V) curve graph under simulated solar irradiation.
Specific implementation mode
In order to make those skilled in the art more fully understand technical scheme 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 be best understood from the disclosure on the contrary, providing these embodiments, and can be by the model of the disclosure
It encloses and is completely communicated to those skilled in the art.
In order to solve problems with existing in the prior art：It 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 cell (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 process：
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 carried2) 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 iodine first ammonium temperature,
130~160 DEG C of iodine carbonamidine temperature), it is 2~4mW/cm that the above-mentioned first step, which has illumination, intensity of illumination,2, 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) can be lead chloride (PbCl2), lead bromide (PbBr2), lead iodide
(PbI2), selenium chloride (SnCl2), selenium bromide (SnBr2) or iodate selenium (SnI2) in one or several kinds of combinations；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
In one or several kinds of combinations, 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), the nitrogenous organic salt halide difference of above two
Belong to the hydriodate of methylamine, carbonamidine.In addition, above-mentioned preparation method be related to prepare product organic ammonium metal halide film
(ABX3) include common several nitrogenous organic salt metal halide photovoltaic materials, such as CH3NH3PbI3。
Specifically, in the above-mentioned preparation method for synthesizing organic inorganic hybridization perovskite thin film using low vacuum, 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
Rapid volatilization, 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 arrive 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) when use isolation air operating method category
In a kind of Low Pressure Chemical Vapor Deposition (LPCVD) technique using parallel to thermal station, metal halide is prepared when using wet method
(BX2) film when, need not use other vacuum evaporation cavitys or vacuum dryer, the invention be low vacuum level technique, can will
After the device extension continuous apparatus is formed with high vacuum vapor deposition cavity.
In addition, in the step 3, according to substrate difference, the reaction time can be selected as 5~40 minutes or 20~50
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：
First, substrate base is cleaned：Cleaning agent, isopropanol, acetone, each ultrasound 20min of deionized water are used respectively, drying
Argon gas dries up, ozone treatment 20 minutes；
Then, by 0.3g PbI2The 80 anhydrous DMI of μ l are dissolved in 0.5mL anhydrous DMFs 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 substrates 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 sprayings
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 the CH at brown3NH3PbI3Film；
Then, heating lower substrate is heated to 110 DEG C, reacts 11min in the case of 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, lower substrate heating and vacuum pump are closed, argon gas is filled with to device, is made and covers on complete, microcosmic by longitudinal direction
Through the CH of crystal grain composition3NH3PbI3Film.
With 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 films 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
The PSCs of method preparation, 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 of a 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 positioned over 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 between 5 and the lid is light accessory channel 6, and the central position of the lid is provided with suprasil
The top of window 7, clear quartz window 7 is 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 applies illumination, device cavity 1 to reactant 3 across upper transparent heat the substrate
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, with the organic ammonium metal halide further to 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 semi-conducting 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 electricity conversion 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 film prepared by this method requires substrate, that is to say, that can be made on arbitrary substrate
The perovskite particle of standby any thickness formed by longitudinally running through crystal grain, this is to improving the electronics device that perovskite is semi-conducting material
The performance of part is very favorable.
Characterizing method three：
Referring to Figure 13, the perovskite solar cell being prepared according to preparation method provided by the invention 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 semi-conducting material.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, what can be readily occurred in changes, equally replaces any one skilled in the art
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 domain asked.
Claims (10)
1. a kind of preparation method of organic ammonium metal halide film, it is characterised in that：Using light auxiliary chemical vapor deposition method
The organic ammonium metal halide film is prepared, step includes：
Step 1 prepares crystallinity in the substrate of precleaning by vacuum evaporation or polar non-solute additive method
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 carries out the first step first, in the case where metal halide film-substrate does not heat, will be had
Machine ammonium halide powder is 2~4mW/cm in intensity of illumination2Illumination condition under be heated to distilling, then carry out second step, will
The metal halide film and the organic ammonium halide powder are heated to 100~160 DEG C and are reacted jointly；
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：It is 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 of organic ammonium metal halide film as described in any one of claim 1-6
It sets, it is characterised in that：Described device includes the device cavity of a cylindrical shape, and the bottom in device cavity is provided with lower heating
Substrate, under the upper surface that heats the substrate be provided with Pbl2Film substrate, Pbl2The upper of the top of film substrate transparent heats the substrate use
To place organic bittern compound, the organic salt halide be positioned over it is transparent heat the substrate and under heat the substrate between, device
The top open part of 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 applies light to the reactant in substrate across upper transparent heat the 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。
9. a kind of characterization is prepared into according to the preparation method of claim 1-6 any one of them organic ammonium metal halide films
The method of the organic ammonium metal halide film product arrived, it is characterised in that：It is aobvious using atomic force microscope or scanning electron
Micro mirror is analyzed and characterized the particle of the organic ammonium metal halide film.
10. a kind of characterization is prepared according to the preparation method of claim 1-6 any one of them organic ammonium metal halide films
The method of obtained organic ammonium metal halide film product, it is characterised in that：According to the organic ammonium metal halide film
Current density-voltage (J-V) curvilinear characteristic under simulated solar irradiation turns the photoelectricity of the organic ammonium metal halide film
Change efficiency to be characterized and analyzed, or using film thickness analytic approach, ultraviolet-visible absorption spectroscopy analytic approach to organic ammonium gold
The quality for belonging to halide film is analyzed.
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| CN110349886A (en) * | 2019-06-19 | 2019-10-18 | 江苏大学 | Large-area perovskite solar cell preparation device and preparation method |
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| CN113845896A (en) * | 2021-09-10 | 2021-12-28 | 天津理工大学 | Curved organic ammonium metal halide film, preparation method, solar cell and application |
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