CN104404478A - Method for preparing organic ammonium metal halide film - Google Patents
Method for preparing organic ammonium metal halide film Download PDFInfo
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- CN104404478A CN104404478A CN201410681219.2A CN201410681219A CN104404478A CN 104404478 A CN104404478 A CN 104404478A CN 201410681219 A CN201410681219 A CN 201410681219A CN 104404478 A CN104404478 A CN 104404478A
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Abstract
The invention discloses a method for preparing an organic ammonium metal halide film. A half-closed type carrier gas free hot wall type low-pressure chemical vapor deposition method process is adopted to prepare the organic ammonium metal halide film. The method comprises the following steps: firstly, preparing a metal halide (MX2) film on a quartz substrate by using a dry method or a wet method, and transferring the metal halide (MX2) film into a glass tube for annealing, wherein one end of the glass tube is sealed and the other end is grounded; secondly, transferring the energy to organic ammonium (AX) powder inside the glass tube through a hot wall, forming steam blocks through self-diffusion of AX steam in low vacuum, performing chemical reaction on MX2 with a hot substrate to generate the film which is uniform in thickness, good in appearance, high in light absorption rate and smooth in surface, and performing in-situ annealing so as to generate the AMX3 film which is dense in structure and high in crystallinity degree. The method has the advantages that in-situ annealing can be performed in the film formation process, continuous vacuuming is not needed, the preparation time is shortened, the energy consumption is reduced, the filming efficiency is high, the charge capture trap in the film is reduced, and the carrier mobility is increased.
Description
[technical field]
The present invention relates to organic inorganic hybridization technical field of semiconductors, be specifically related to a kind of preparation method of organic ammonium metal halide film.
[background technology]
Organic inorganic hybridization organic ammonium metal halide (AMX
3) normally uhligite crystal formation, be therefore also called organic-inorganic perovskite compound (IOP).AMX
3normally by metal halide (MX
2) and organic ammonium halogenide (AX) two kinds of component synthesis.Photovoltaic technology develops a kind of novel renewable energy rapidly recently in decades.Along with the progress of technology, its photoelectric transformation efficiency is greatly improved.The laminated cell be wherein made up of GaAs/InP, the highest transformation efficiency reaches 44.7%.The solar battery efficiency be made up of crystal silicon reaches 25%, and the sun power efficiency be made up of copper-indium-galliun-selenium (CIGS) reaches 21%.Although above conventional solar cell efficiency is higher, preparation cost is relatively high.Organic solar batteries, dye sensitization solar battery, quantum dot solar cell, perovskite typed solar cell etc. are the very popular photovoltaic technologies occurred in recent years.By AMX
3the thin-film solar cells formed as active coating is the topic that area of solar cell one is very popular in recent years.Such battery is commonly called perovskite typed solar cell (PSC).The most high-photoelectric transformation efficiency of perovskite typed solar cell, by the interface engineering of research film, is brought up to 19.3% by the Y.Yang team of Univ California-Los Angeles USA.The efficiency of uhligite solar cell is at present still in quick growth.
The solution preparation of perovskite thin film is divided into single step solution method and two step solution methods.The preparation method of single step solution method is normally: by MX
2, AX is dissolved in solvent (as gamma-butyrolactone), is then prepared film forming by wet method.Last anneal.The first method of two step solution methods is normally: first by MX
2be dissolved in respectively with AX and intersect accordingly in solvent (as DMF and Virahol).The wet methods such as spin coating are utilized to make MX
2film, then same wet method makes one deck AX film thereon, and in making AX thin-film process, AX molecule infiltrates the MX of lower floor
2in film, with its reaction, obtain one deck and contain AMX
3, solvent, MX
2, AX mixed film.Finally utilize thermal annealing process to remove desolventizing, promote MX
2with the reaction of AX, thus obtain the high AMX of degree of crystallinity
3film.The second method of two step solution methods is: by the MX made above
2film immerses in AX solution, and solute molecule spreads in liquid-solid interface, reaction.The soak time of the method is generally 1-3 hour.In immersion process, the perovskite thin film that initial surface is formed can be partly solubilized, and is thus difficult to obtain smooth film.The common drawback of wet method perovskite film accurately cannot control thickness, is difficult to the film obtaining surface uniform, is difficult to make rhythmo structure etc.
The method of vapour deposition can overcome above shortcoming, and these class methods reported at present comprise the source vapour deposition of vacuum list, the vapour deposition of vacuum double source, inert gas carrier chemical vapour deposition and gas phase and assist aumospheric pressure cvd four kinds.1999, the people such as the D.B.Mitzi of American I BM company utilized the vapour deposition of vacuum list source to make AMX
3film, employing be single source flash method (SSTA).Flash method has the shortcomings such as accurately cannot control thickness and evaporation rate is slow, thus cannot be applied in quick scale operation.2013, the H.J.Snaith seminar of Regius professor utilized vacuum double source vapour deposition process to make AMX
3film.The film that the method is made has very high planeness, and its particle diameter is more than some tens of pm.The photovoltaic device photoelectric transformation efficiency be made up of this film can reach 15.4%.But the shortcoming of the method is because AX molecule has very low vaporization temperature, at the vaporization temperature, first AX is decomposed into organic amine and hydrogen halide (note: under normal pressure, AX can distil but not decompose.
4), cause huge pollution to wall inside, the method cannot carry out scale operation.2014, the D.J.Lewis seminar of Britain's this especially big of graceful side utilized aerosol assistant chemical vapor deposition (AACVD) fabrication techniques perovskite thin film.The defect of the method is the surface topography being difficult to control film, is difficult to uniformly film (scheming see its SEM).2014, the Y.Qi seminar of university of Okinawa Japan science and technology large institute utilized mixed chemical vapour deposition process (HCVD) to prepare AMX
3film, the advantage of the method is that film-forming properties is even, and thickness is controlled.But the shortcoming of the method is difficult to control to the actual Heating temperature of substrate.Meanwhile, this system uses the conventional CVD process of open system, and AX is taken to MX by rare gas element
2surface is reacted, and thus system air pressure is higher, and AX steam mean free path is short, speed of reaction is slow, diffractive difference.In addition, the common feature of above CVD (Chemical Vapor Deposition) method adopts vacuum as reaction environment, and reaction process intermediate pump is in running order all the time, thus there is the shortcomings such as energy expenditure is large, production cost is high.2014, the Y.Yang team of Univ California-Los Angeles USA had been full of N by utilizing
2glove box in heating AX (CH in closed system
3nH
3i), by advance by MX prepared by spin coating
2(PbI
2) film is converted into AMX
3(CH
3nH
3pbI
3) film.With the film that the method generates, there is PbI
2transformation efficiency is high, uniform particles, coverage advantages of higher.But due in the method, PbI
2the surface of film and particulate interspaces are filled with the nitrogen molecule not participating in reacting, and these nitrogen molecules make the CH arriving film surface
3nH
3the mean free path of I vapour molecule is less than several CVD method above-mentioned several order of magnitude, therefore can collide out AX vapour molecule, be difficult to arrive film substrate.Generally need reaction times (two hours) of more growing in this way, this is unfavorable to quick scale operation.
Low Pressure Chemical Vapor Deposition (LPCVD) is compared to atmospheric pressure cvd (NPCVD), and LPCVD has advantages such as improving uniformity of film, resistivity consistence and production efficiency.Its reason is that LPCVD is owing to having lower pressure, thus has lower molecular conecentration, higher spread coefficient, faster quality transmission rate, faster speed of reaction, the reaction advantage such as more abundant.In addition, traditional C VD method is usually because high temperature problem cannot use on flexible substrates.It is temperature required low that the organic ammonium raw material of the organic ammonium metal halide that the present invention relates to forms the steam being applicable to reacting, and thus can synthesize on flexible substrates.
The comparison of the various AMX3 method for manufacturing thin film of form 1
*, the raw material availability of * * spin-coating method is low, silk screen printing, and the raw material availabilities such as volume to volume printing are high
+ need to react in glove box
++ what part document was mentioned prepares speed
#, ## can be improved by solvent engineering
[summary of the invention]
The object of the invention is for above-mentioned technical Analysis and existing problems, provide a kind of preparation method of organic ammonium metal halide film, this preparation method improves the mean free path of vapour molecule, thus makes reaction more fully fast; Film is ingress of air not, and film equality, density are high; In deposition process, do not need vacuum pump continued running, do not need inert gas carrier, AX raw material recoverable, can significantly reduce the energy and carrier gas cost drop into, be applicable to scale operation
Technical scheme of the present invention:
A preparation method for organic ammonium metal halide film, adopts semienclosed no carrier gas hot wall type Low Pressure Chemical Vapor Deposition (HW-LPCVD) technique to prepare, comprises the following steps:
1) under the condition of isolated air, in the substrate cleaned up, metal halide (MX is prepared by wet method or dry method
2) film, the cavity of load sample is vacuumized, vacuum tightness be 0.1-1000Pa, temperature be 60-100 degree Celsius under by sample holder to MX
2film carries out annealing 5-10 minute to remove residual solvent and foreign gas, heats 5-10 minute to remove the foreign gas of inside cavity absorption at 60-100 DEG C of temperature simultaneously;
2) film sample of preparation and organic ammonium halogenide (AX) powder are placed in the cavity of load sample, at temperature is 110-200 DEG C, reacts 10-30 minute;
3) specimen holder is stopped to heat after reacting completely;
4) obtained AMX
3film, is filled with rare gas element and preserves.
Described metal halide (MX
2) material is lead chloride (PbCl
2), lead bromide (PbBr
2), lead iodide (PbI
2), Selenium monochloride, Selenium monobromide or iodate selenium; Organic ammonium halogenide (AX) material is chloromethane ammonium, chloroethene ammonium, chlorine formamidine salt (NH=CHNH
3cl), chlorine dimethylammonium, bromine first ammonium, bromine second ammonium, bromine formamidine salt (NH=CHNH
3br), bromine dimethylammonium, iodine first ammonium, iodine second ammonium, iodine formamidine salt (NH=CHNH
3or iodine dimethylammonium I).
A kind of preparation facilities of described organic ammonium metal halide film, comprise Glass tubing, specimen holder, heating jacket and feed-pipe, one end of Glass tubing is provided with sealing plug, be provided with middle part sealing plug in the middle of Glass tubing and Glass tubing be divided into annular seal space a and annular seal space b, sealing plug center, middle part is provided with centre hole, the annular seal space b part of Glass tubing is provided with bleeds ventpipe and is provided with seal cartridge, and the exit end of Glass tubing is provided with vapor pipe and is provided with valve; Specimen holder is arranged in the annular seal space a of Glass tubing; The annular seal space a that heating jacket is arranged at Glass tubing is outside; Feed-pipe enters in annular seal space a through the centre hole of bleed ventpipe and middle part sealing plug.
Technical Analysis of the present invention:
Rough vacuum is utilized to synthesize organic ammonium metal halide film, vacuum tightness in Glass tubing is 0.1-1000Pa, do not need vacuum pump still can maintain vacuum tightness required for reaction after chamber vacuum degree is evacuated to required vacuum tightness, the joule heating transferring energy utilizing hot-plate to produce is to hot wall, directly act on AX raw material, make it form steam.In the inner collision continuously of wall, there is diffraction in AX steam.The diffusion of AX molecule bears free energy change by the temperature at non-heated position, two ends to drive, but not vacuum pump takes out the diffusion or inert carrier gas (N that cause
2or Ar etc.) transport.Energy can be saved like this.
Utilize inside and outside two temperature-control devices control MX respectively
2the temperature in backside of substrate temperature and AX source synthesizes organic ammonium metal halide film.AX is dispersed in the Glass tubing bottom in external heat interval range, utilizes hot wall to heat and evaporates.MX
2substrate is attached on specimen holder, is positioned between outer heating zone equally, but is directly heated by specimen holder.Thus can to MX
2annealing and after annealing process in original position preannealing, reaction process is accurately carried out in substrate.Thus ensure that the homogeneity of film former, impurity defect is reduced, decreases the time cost of sample transfer simultaneously.
The present invention is at preparation AMX
3what adopt during film is the working method completely cutting off air completely, is semienclosed no carrier gas hot wall type Low Pressure Chemical Vapor Deposition (HW-LPCVD) technique of a kind of employing.As employing wet-layer preparation MX
2during film, do not need to use other vacuum evaporation cavity or vacuum dryers, rear for the extension of this device and glove box can be formed continuous apparatus.As employing dry process MX
2during film, rear for the extension of this device and vacuum evaporation cavity can be formed continuous apparatus.
The invention has the beneficial effects as follows:
1, the heat that hot wall produces is efficiently utilized, and makes evaporation source AX form steam, and makes the steam of generation in wall inside not condensation, improve the diffractive of AX molecule, can form the collision that repeatedly rebounds, until and MX in wall inside
2reaction or the region condensation colder at two ends;
2, carry out In Situ Heating by specimen holder to film, molecular motion is violent, and lattice mismatch degree is little.The perovskite thin film subsurface defect produced is few, and degree of crystallinity is high; But the temperature of specimen holder can not be too high, otherwise organic ammonium molecule is difficult to adsorb at film surface, and on the other hand, the crystal grain generated under high temperature is large, affects planeness; Meanwhile, base reservoir temperature can not be too low, otherwise excessive organic ammonium molecule at film surface and specimen holder surface condensation, can affect its diffusion and further reaction;
3, wall inside can be recycled at the AX compared with cold spots condensation, reduces cost of manufacture;
4, AMX
3formation belong to gas-solid out-phase reaction, gas molecule has higher mean free path relative to fluid molecule, and therefore relative to liquid phase reaction, AX is at MX
2the velocity of diffusion of solid particulate interface and granule interior is faster, and speed of reaction is faster, reaction is more abundant.
5, because two kinds of reaction meet stoichiometric between raw material and the material of generation, produce, thus without the need to inert gas carrier without gas by-product; Meanwhile, because temperature of reaction is lower, thus without the need to reacting in the closed quartz tube of harshness, semi-enclosed Glass tubing and the supporting system of silica gel material can meet reaction conditions.Economy, operability, preparation efficiency improve greatly.No carrier gas, semi-enclosed LPCVD preparation method of use low vacuum do not see and prepared AMX in the past
3in the relevant report of film.
This device has the feature of exclusion of water oxygen, thus can improve the AMX of formation
3the aerial stability of film.The present invention preparation method used have be swift in response, film forming evenly, fine and close, energy expenditure is low, rare gas element consumption less, the feature such as thickness is controlled, be very applicable to large scale continuous prod.
[accompanying drawing explanation]
Fig. 1 is the preparation facilities structural representation of this organic ammonium metal halide film.
Fig. 2 is the amplification perspective view of the specimen holder of the preparation facilities of organic ammonium metal halide film.
In figure: 1. in the middle part of Glass tubing 2. specimen holder 3. heating jacket 4. feed-pipe 5. sealing plug 6., sealing plug 7. annular seal space a 8. annular seal space b 9. centre hole 10 is bled ventpipe 11. seal cartridge 12. vapor pipe 13. valve.
Fig. 3 is the CH that in embodiment 1 prepared by no carrier gas hot wall type Low Pressure Chemical Vapor Deposition
3nH
3pbI
3the PbI that surface topography AFM figure (left side) of film and corresponding wet method obtain
2the surface topography AFM of film schemes (right side).
Fig. 4 is the CH that in embodiment 1 prepared by no carrier gas hot wall type Low Pressure Chemical Vapor Deposition
3nH
3pbI
3the PbI that the XRD spectra of film differential responses time and corresponding wet method obtain
2the XRD spectra of film.
Fig. 5 is the CH that in embodiment 1 prepared by no carrier gas hot wall type Low Pressure Chemical Vapor Deposition
3nH
3pbI
3the PbI that the visible absorption spectra figure of film and corresponding wet method obtain
2the visible absorption spectra figure of film.
Fig. 6 is the CH that in embodiment 2 prepared by no carrier gas hot wall type Low Pressure Chemical Vapor Deposition
3nH
3pbI
3the film thickness of different zones eight points of different positions on the substrate of 1 inch × 1 inch of film.
Fig. 7 is the CH that in embodiment 2 prepared by no carrier gas hot wall type Low Pressure Chemical Vapor Deposition
3nH
3pbI
3the PbI that surface topography SEM figure (left side) of film and corresponding dry method obtain
2the surface topography SEM of film schemes (right side).
Embodiment
Following examples will the present invention is described further by reference to the accompanying drawings.In following examples, the preparation of target compound all utilizes the preparation facilities of organic ammonium metal halide film to complete.The preparation facilities of this organic ammonium metal halide film, as shown in Figure 1, 2, comprise Glass tubing 1, specimen holder 2, heating jacket 3 and feed-pipe 4, one end of Glass tubing 1 is provided with sealing plug 5, be provided with middle part sealing plug 6 in the middle of Glass tubing 1 and Glass tubing be divided into annular seal space a7 and annular seal space b8, sealing plug center, middle part is provided with centre hole 9, and the annular seal space b8 part of Glass tubing 1 is provided with bleeds ventpipe 10 and is provided with seal cartridge 11, and the exit end of Glass tubing 1 is provided with vapor pipe 12 and is provided with valve 13; Specimen holder 2 is arranged in the annular seal space a7 of Glass tubing 1; The annular seal space a7 that heating jacket 3 is arranged at Glass tubing 1 is outside; Feed-pipe 4 enters in annular seal space a7 through the centre hole 9 of bleed ventpipe 10 and middle part sealing plug 6.
Embodiment 1:
A preparation method for organic ammonium metal halide film, adopts semienclosed no carrier gas hot wall type Low Pressure Chemical Vapor Deposition (HW-LPCVD) technique to prepare, comprises the following steps:
1) quartz plate is cleaned: use acetone, Virahol, deionized water ultrasonic cleaning quartz plate 30 minutes respectively, pressurized air dries up, ozonize 10 minutes; By 0.23g PbI
2be dissolved in 0.5mL dry DMF, be heated to 60 DEG C, magnetic agitation 30 minutes; On the 2.5cm × 2.5cm silica glass cleaned up, 6000rpm spin coating PbI
2dMF solution 30s; Heating 5 minutes in thermal station substrate being placed in 100 DEG C, after naturally cooling to room temperature, the PbI good by spin coating
2quartz plate is transferred to and is full of in the glove box of argon gas.
2) preparation facilities put into glove box and open valve, taking 0.02 gram of CH
3nH
3i, evenly puts into heating jacket overlay area.
3) by PbI
2quartz plate is attached on specimen holder.Put into annular seal space a, close total valve and seal cartridge valve, preparation facilities is transferred to outside glove box.
4) pass into high-purity argon gas from valve, connect vacuum meter, with biexhaust pipe, device device is bled, use hair dryer water back simultaneously, get rid of the water vapour of inwall absorption, be then filled with high-purity argon gas, repeatedly pumping-charge operation three times.
5) open valve, be filled with high-purity argon gas, be evacuated to below 1000Pa; Valve-off, wait for 20 minutes, as vacuum tightness is undamped, then identity system is without gas leakage.Open valve, heated sample frame to 100 DEG C, wait for 5 minutes, carry out degasification and vacuum pre-anneal treatment.
6) open heating mantle heats system, be heated to 80 DEG C, wait for 10 minutes, system degasification, is then increased to 120 DEG C by jacket temperature, stops 1 minute, further degasification, valve-off; Continue to be increased to 150 DEG C, stop 10 minutes, CH in this process
3nH
3i forms steam and and PbI
2react, generate rapidly the CH of chocolate
3nH
3pbI
3film.
7) close heating mantle heats system, remove heating jacket, exposed by annular seal space a outer wall and naturally cool to room temperature in atmosphere, be then filled with high-purity argon gas, valve-off, obtained organic ammonium metal halide film, film thickness gauge records thickness and is about 450nm.
Fig. 3 is CH prepared by no carrier gas hot wall type Low Pressure Chemical Vapor Deposition
3nH
3pbI
3the PbI that surface topography AFM figure (left side) of film and corresponding wet method obtain
2the surface topography AFM of film schemes (right side).Show in figure: CH
3nH
3pbI
3particle diameter is 100-450nm, covers quartz surfaces substantially completely, and its mean square roughness is 33.0nm, is about PbI
2three times of mean square roughness (10.3nm).
Fig. 4 is CH prepared by no carrier gas hot wall type Low Pressure Chemical Vapor Deposition
3nH
3pbI
3the PbI that the XRD spectra of film differential responses time and corresponding wet method obtain
2the XRD spectra of film.Show in figure: the XRD spectra of reacting 10 minutes, 30 minutes, 60 minutes, 120 minutes is basically identical, all without PbI
2peak occurs, shows in 10 minutes, most PbI
2react and generated CH
3nH
3pbI
3.
Fig. 5 is CH prepared by no carrier gas hot wall type Low Pressure Chemical Vapor Deposition
3nH
3pbI
3the PbI that the visible absorption spectra figure of film and corresponding wet method obtain
2the visible absorption spectra figure of film.Show in figure: the CH of generation
3nH
3pbI
3the photoabsorption interval of film extends to 760nm, covers whole visible region, is suitable as light absorbing zone.
Embodiment 2:
A kind of preparation method of organic ammonium metal halide film, semienclosed no carrier gas hot wall type Low Pressure Chemical Vapor Deposition (HW-LPCVD) technique is adopted to prepare, step is substantially the same manner as Example 1, and difference is that the purging method of quartz plate is as follows:
Use acetone, Virahol, deionized water ultrasonic cleaning quartz plate 30 minutes respectively, pressurized air dries up, ion bombardment 10 minutes; 5 × 10
-4under Pa background pressure, with the speed of 0.1nm/s, the 2.5cm × 2.5cm quartz cleaned up is prepared the PbI of one deck 80nm
2film, source cardinal distance is 40cm, and source is loaded on tungsten boat, and substrate distribution adopts rotary spherical distribution, and its thickness is controlled by corrected quartz crystal.Base reservoir temperature is 80 DEG C, then by PbI
2quartz plate is transferred to and is full of in the glove box of argon gas.
Fig. 6 is CH prepared by no carrier gas hot wall type Low Pressure Chemical Vapor Deposition
3nH
3pbI
3the film thickness of different zones eight points of different positions on the substrate of 1 inch × 1 inch of film, shows in figure: the thickness of A-H point is followed successively by 231nm, 226nm, 235nm, 230nm, 227nm, 235nm, 231nm, 225nm.
Fig. 7 is CH prepared by no carrier gas hot wall type Low Pressure Chemical Vapor Deposition
3nH
3pbI
3the PbI that surface topography SEM figure (left side) of film and corresponding dry method obtain
2the surface topography SEM of film schemes (right side).Show in figure: PbI
2film in the form of sheets, and generate CH
3nH
3pbI
3film is formed primarily of particle, and particle diameter ratio is comparatively even, and particle diameter is 200-400nm, covers quartz surfaces substantially completely.
Above-mentioned embodiment is only that the present invention's enforceable small-scale in laboratory scale prepares AMX
3the preferred implementation of film; describe technological line of the present invention and essential implementation in detail; not that protection scope of the present invention is limited; all any simple modification of carrying out according to spirit of the present invention and equivalent structure transformation or modification, all should be encompassed within protection scope of the present invention.
Known to the thickness distribution of film, crystalline structure, Analysis of Surface Topography by means of testing such as step instrument, X-ray diffraction (XRD), atomic force microscope (AFM), scanning electronic microscope (SEM), absorption spectrometers: the method applied in the present invention can prepare the perovskite typed AMX that thickness is even, degree of crystallinity is high, light absorption ratio is high
3film.The method that the present invention adopts solves film morphology AMX
3the dynamics problem of building-up reactions.For AMX
3the formation of film, its speed of reaction mainly by AX molecule at MX
2rate of diffusion in crystal grain determines, with the saturation vapour pressure of AX, mean free path, base reservoir temperature and MX
2the pattern of film is relevant.Improve the saturation vapour pressure of AX, reduce background pressure, improve base reservoir temperature and can improve rate of diffusion and speed of reaction.Directly contacted with hot wall by (1), under (2) rough vacuum condition, (3) substrate In Situ Heating three approach implements simultaneously, speed of reaction is accelerated greatly, effectively shortens the reaction times.
Claims (3)
1. a preparation method for organic ammonium metal halide film, is characterized in that: adopt semienclosed no carrier gas hot wall type Low Pressure Chemical Vapor Deposition (HW-LPCVD) technique to prepare, comprise the following steps:
1) under the condition of isolated air, in the substrate cleaned up, metal halide (MX is prepared by wet method or dry method
2) film, the cavity of load sample is vacuumized, vacuum tightness be 0.1-1000 Pa, temperature be 60-100 degree Celsius under by sample holder to MX
2film carries out annealing 5-10 minute to remove residual solvent and foreign gas, heats 5-10 minute to remove the foreign gas of inside cavity absorption at 60-100 DEG C of temperature simultaneously;
2) film sample of preparation and organic ammonium halogenide (AX) powder are placed in the cavity of load sample, at temperature is 110-200 DEG C, reacts 10-30 minute;
3) specimen holder is stopped to heat after reacting completely;
4) obtained AMX
3film, is filled with rare gas element and preserves.
2. the preparation method of organic ammonium metal halide film according to claim 1, is characterized in that: described metal halide (MX
2) material is lead chloride, lead bromide, lead iodide, Selenium monochloride, Selenium monobromide or iodate selenium; Organic ammonium halogenide (AX) material is chloromethane ammonium, chloroethene ammonium, chlorine formamidine salt (NH=CHNH
3cl), chlorine dimethylammonium, bromine first ammonium, bromine second ammonium, bromine formamidine salt (NH=CHNH
3br), bromine dimethylammonium, iodine first ammonium, iodine second ammonium, iodine formamidine salt (NH=CHNH
3or iodine dimethylammonium I).
3. the preparation facilities of an organic ammonium metal halide film as claimed in claim 1, it is characterized in that: comprise Glass tubing, specimen holder, heating jacket and feed-pipe, one end of Glass tubing is provided with sealing plug, be provided with middle part sealing plug in the middle of Glass tubing and Glass tubing be divided into annular seal space a and annular seal space b, sealing plug center, middle part is provided with centre hole, the annular seal space b part of Glass tubing is provided with bleeds ventpipe and is provided with seal cartridge, and the exit end of Glass tubing is provided with vapor pipe and is provided with valve; Specimen holder is arranged in the annular seal space a of Glass tubing; The annular seal space a that heating jacket is arranged at Glass tubing is outside; Feed-pipe enters in annular seal space a through the centre hole of bleed ventpipe and middle part sealing plug.
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| CN105470400A (en) * | 2015-11-19 | 2016-04-06 | 华北电力大学 | Perovskite film preparation method and application |
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