CN105702871A - Method for preparing perovskite thin film in perovskite solar cell via solution air extraction and ventilation method - Google Patents
Method for preparing perovskite thin film in perovskite solar cell via solution air extraction and ventilation method Download PDFInfo
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Abstract
The invention provides a method for preparing a perovskite thin film in a perovskite solar cell via a solution air extraction and ventilation method. The method comprises the following steps: a perovskite liquid film coated on a surface of a base body is subjected to air extracting and drying operation in an environment where the partial pressure of the solvent is lower than 99% saturated vapor pressure of the solvent at current temperature; during drying processes or after the perovskite liquid film is completely dries, a gas which does not react chemically with a perovskite is let in, and therefore a process that the solvent is evaporated or solvent molecules leave the environment can be accelerated via solvent molecule concentration dilution. Heterogeneous nucleation and growth of the surface of the base body can be realized via control over drying process conditions, and therefore a uniform and compact perovskite thin film can be formed. The method can be used for accelerating liquid film drying processes, making solvent steam molecules leave a surface of the thin film quickly, and obtaining the uniform-structured and compact perovskite thin film; thus current leakage caused by perovskite thin film loopholes can be prevented and the method can help make high-efficiency solar cells; the method is advantaged by simple operation, easy-to-implement property, low cost, high repetition accuracy, convenience for industrialization and the like.
Description
Technical field
The invention belongs to material science and technology, film preparing technology and solaode preparing technical field, be specifically related to a kind of utilize solution venting method of bleeding to prepare the method for perovskite thin film in perovskite solaode。
Background technology
At photovoltaic art, having the organic-metallic halogenide of perovskite structure as a kind of light absorbing material, cause the very big concern of photovoltaic circle with the character of its uniqueness, the conversion efficiency of perovskite solaode was advanced by leaps and bounds in recent years, more than 20%。Perovskite thin film, as opto-electronic conversion stock in perovskite solaode, is key and the core of perovskite solaode, and its preparation technology mainly adopts solwution method, wherein comprises one-step method and two-step method。Though one-step method operates relatively easy, but there are some problems in the perovskite thin film of preparation: the uniformity of thin film and crystallinity can not be effectively controlled, perovskite thin film coarse grains, in dendroid, the coverage rate of matrix is low, cause electronics extremely easy and hole generation compound in transmitting procedure, cause perovskite solar cell properties poor and stability is good not。Obtaining perovskite thin film uniform, fine and close, that bond strength is good, coverage rate is high is the key preparing high performance calcium titanium ore solaode。The condition of liquid phase crystallization is that solution has degree of supersaturation。Existing technical scheme is mainly by the natural drying of solvent in solution or direct drying, it is difficult to realizing the good control to perovskite thin film crystallization property, therefore one-step method cannot obtain the perovskite thin film of even compact。Have been reported that and accelerate evaporation by air-blowing, solution rate of drying can be improved to a certain extent, but it is unstable that air-blowing easily causes solution face, thus causing perovskite thin film surface undulation uneven, it is likely to result in matrix exposed, affect perovskite solaode uniformity and photoelectric properties, it is difficult to commercial application。
Summary of the invention
It is an object of the invention to provide and a kind of utilize solution venting method of bleeding to prepare the method for perovskite thin film in perovskite solaode, the shortcoming that the method can overcome prior art, it is thus achieved that the perovskite thin film that even structure is fine and close。
For reaching above-mentioned purpose, the technical solution used in the present invention is:
A kind of solution venting method of bleeding is utilized to prepare the method for perovskite thin film in perovskite solaode, it concretely comprises the following steps: perovskite solution is coated in matrix surface, form perovskite liquid film, then be placed in low solvent partial pressure environment to carry out bleed dry, when bleeding dry, the temperature of perovskite liquid film is between the freezing point temperature and boiling temperature of solvent, in dry run or be completely dried and pass into gas afterwards, in the way of retarder thinner molecular concentration, accelerate solvent evaporation or solvent molecule leaves this environment, in dry run, control drying condition simultaneously, the solute in perovskite liquid film is made at matrix surface out-phase forming core and to grow, obtain uniformly, fine and close perovskite thin film；Wherein low solvent partial pressure environment refers to that the solvent partial pressure in this environment is lower than solvent saturated vapor pressure of 99% under current baking temperature, solvent partial pressure in the gas passed into is lower than the solvent partial pressure in this environment current, and this gas does not react with perovskite liquid film or thin film, described solvent is the solvent in perovskite solution。
The described mixed solvent that the solvent in perovskite solution is one or both arbitrary proportions in DMF, DMSO or γ-Ding lactone；Solute in perovskite solution is mol ratio is the PbX of 1:12And CH3NH3Y, wherein X is I, Br or Cl, and Y is I, Br or Cl, and X and Y is identical or different。
PbX in described perovskite solution2And CH3NH3Y shape becomes CH3NH3PbX2Y, CH3NH3PbX2The mass percentage concentration of Y is 10～50%。
Perovskite solution is coated in matrix surface by the mode adopting blade coating, spraying or coating, the thickness≤5000nm of the perovskite liquid film obtained。
The temperature controlling perovskite solution when bleeding dry is-20～40 DEG C。
Solvent partial pressure in the gas passed in dry run is less than in current low solvent partial pressure environment the 80% of solvent partial pressure, and being completely dried the solvent partial pressure in the gas passed into afterwards is in current low solvent partial pressure environment the 50%～0 of solvent partial pressure。
Controlling drying condition makes the solute in perovskite liquid film at matrix surface out-phase forming core and grow, refer to by the control to matrix rough morphology, heat compensation, the speed of evacuation and rate of drying, suppress homogenous nucleation in perovskite liquid film, make solute at the preferential out-phase forming core of matrix surface, and continue crystallization, grow into the perovskite thin film of dense uniform。
Described out-phase forming core, is when the matrix adopting surface smooth, at the uniform out-phase forming core of matrix surface；
Described out-phase forming core, is when adopting coarse matrix, crystalline core size less than matrix rough surface dimple size when, the preferential out-phase forming core at pit position；Or crystalline core size more than matrix rough surface dimple size when, at the uniform out-phase forming core of rough surface。
Described heat compensation is, by the mode of substrate preheating or heating, the preheating of perovskite liquid film or heating or contactless radiation heating, perovskite liquid film or matrix are carried out instant heat compensation。
After bleeding and having dried, the thin film obtained is carried out at 57～300 DEG C the heat treatment of 2min～10h, namely obtains perovskite thin film。
Relative to prior art, the invention have the benefit that
Provided by the invention solution venting method of bleeding is utilized to prepare the method for perovskite thin film in perovskite solaode, the perovskite liquid film of matrix surface will be coated in, it is dry lower than carrying out in the environment of the saturated vapor pressure of 99% under solvent Current Temperatures bleeding to be placed in solvent partial pressure, in dry run or after being completely dried, pass into solvent partial pressure lower than when in environment solvent partial pressure and not with the gas of perovskite generation chemical reaction, to significantly reduce current solvent partial pressure, leave environment by accelerating solvent evaporation or solvent molecule in the way of retarder thinner molecular concentration。Simultaneously in dry run, by controlling rate of drying, matrix surface is made based on out-phase forming core crystallization and to grow, thus generating the perovskite thin film of dense uniform。Although by reducing pressure to the saturated vapor pressure of solvent under Current Temperatures 99%, add quick-dissolving agent evaporation, make solution quickly have high degree of supersaturation so that a large amount of solute can on matrix out-phase forming core growing, it is possible to obtain comparatively dense perovskite thin film。But, still have partial solvent steam being deposited in thin film surrounding when pumping process terminates, this will cause that the solvent thin film to generating produces corrosion or solvent ageing behavior, affect film quality, reduce battery performance and be likely to damage battery long-time stability。In order to make the solvent vapo(u)r of evaporation quickly leave the film surface of generation in the present invention, to avoid the solvent thin film to generating to produce corrosion or solvent ageing behavior, in dry run or be completely dried the gas passing into solvent partial pressure afterwards lower than current environment internal solvent dividing potential drop, to significantly reduce when the solvent partial pressure in environmental chamber, so that solvent evaporates rapidly or leaves film surface。The present invention can overcome the deficiency that prior art exists, liquid film drying can be accelerated, and make solvent vapo(u)r molecule quickly leave film surface, and obtain the perovskite thin film that even structure is fine and close, thus avoiding the current leakage that perovskite thin film leak causes, be advantageously implemented the manufacture of high performance solar batteries, have simple to operate be easily achieved, with low cost, repeat that accuracy is high, be easy to the advantages such as industrialization。
Further, in the present invention, in dry run of bleeding, in order to further speed up solvent volatilization and the perovskite crystal grain generated be carried out appropriate regulation, it is possible at moderate temperatures thin film is carried out heat treatment, finally give desirable perovskite thin film。Meanwhile, in dry run, it is possible to by the mode of substrate preheating or heating, solution preheating or heating, contactless radiation heating, solution film or matrix are carried out instant heat compensation, to suppress because solution cooling reduces saturated vapor pressure thus affecting rate of drying。And through the dry perovskite thin film obtained of bleeding, it is possible to it is carried out heat treatment, with its grainiess of further optimising and adjustment, pattern and size。
Accompanying drawing explanation
Fig. 1-1 is the CH that comparative example 1 prepares3NH3PbI3The SEM figure of thin film, wherein the amplification of (a) is 5,000 times, and the amplification of (b) is 10,000 times, and the amplification of (c) is 20,000 times。
Fig. 1-2 is the CH that comparative example 2 prepares3NH3PbI3The SEM figure of thin film, wherein the amplification of (a) is 5,000 times, and the amplification of (b) is 10,000 times, and the amplification of (c) is 20,000 times。
Fig. 1-3 is the CH that comparative example 3 prepares3NH3PbI3The SEM figure of thin film, wherein the amplification of (a) is 5,000 times, and the amplification of (b) is 10,000 times, and the amplification of (c) is 20,000 times。
Fig. 2-1 is the CH that comparative example 4 prepares3NH3PbI3The SEM figure of thin film, wherein the amplification of (a) is 5,000 times, and the amplification of (b) is 10,000 times, and the amplification of (c) is 20,000 times。
Fig. 2-2 is the CH that comparative example 5 prepares3NH3PbI3The SEM figure of thin film, wherein the amplification of (a) is 5,000 times, and the amplification of (b) is 10,000 times, and the amplification of (c) is 20,000 times。
Fig. 2-3 is the CH that comparative example 6 prepares3NH3PbI3The SEM figure of thin film, wherein the amplification of (a) is 5,000 times, and the amplification of (b) is 10,000 times, and the amplification of (c) is 20,000 times。
Fig. 3-1 is the CH that embodiment 1 prepares3NH3PbI3The SEM figure of thin film, wherein the amplification of (a) is 5,000 times, and the amplification of (b) is 10,000 times, and the amplification of (c) is 20,000 times。
Fig. 3-2 is the CH that embodiment 2 prepares3NH3PbI3The SEM figure of thin film, wherein the amplification of (a) is 5,000 times, and the amplification of (b) is 10,000 times, and the amplification of (c) is 20,000 times。
Fig. 3-3 is the CH that embodiment 3 prepares3NH3PbI3The SEM figure of thin film, wherein the amplification of (a) is 5,000 times, and the amplification of (b) is 10,000 times, and the amplification of (c) is 20,000 times。
Detailed description of the invention
Perovskite thin film is as the core that the light absorbent of perovskite solaode is perovskite battery, therefore, and one of key being prepared by development high performance solar batteries of high-quality perovskite thin film。The deficiency that the present invention exists in order to avoid prior art, invent a kind of new method preparing perovskite thin film, the perovskite liquid film of matrix surface will be coated in, it is dry lower than carrying out in the environment of the saturated vapor pressure of 99% under solvent Current Temperatures bleeding to be placed in solvent partial pressure, in dry run or be completely dried pass into afterwards solvent partial pressure lower than when front chamber's internal solvent dividing potential drop and not with the gas of perovskite generation chemical reaction, thus accelerating solvent evaporation in the way of by retarder thinner molecular concentration or solvent molecule leaves environment, make matrix surface out-phase forming core by control drying condition and grow in dry run simultaneously, thus being formed uniformly, fine and close perovskite thin film。The present invention can accelerate liquid film drying, and make solvent vapo(u)r molecule quickly leave film surface, and obtain the perovskite thin film that even structure is fine and close, thus avoiding the current leakage that perovskite thin film leak causes, be advantageously implemented the manufacture of high performance solar batteries, have simple to operate be easily achieved, with low cost, repeat that accuracy is high, be easy to the advantages such as industrialization。
The present invention is mainly by below reduction pressure to the saturated vapor pressure of Current Temperatures solvent 99%, add quick-dissolving agent evaporation, make solution quickly have high degree of supersaturation so that a large amount of solute can on matrix out-phase forming core growing, obtain perovskite thin film one layer fine and close。Simultaneously in dry run or after being completely dried, pass into solvent partial pressure lower than when in environment solvent partial pressure and not with the gas of perovskite generation chemical reaction, environment is left by accelerating solvent evaporation or solvent molecule in the way of retarder thinner molecular concentration, the solvent vapo(u)r making evaporation quickly leaves the film surface of generation, to avoid the solvent thin film to generating to produce corrosion or solvent ageing behavior。In order to further speed up solvent volatilization and to the perovskite crystal grain heat treatment generated, it is possible to properly increase Current Temperatures, finally give desirable perovskite thin film。
Described to be placed in solvent partial pressure dry lower than carrying out in the environment of the saturated vapor pressure of 99% under solvent Current Temperatures bleeding, and is undertaken bleeding dry by this environment connects the mode of air pump or the less container of other pressure。
Described in dry run or be completely dried and pass into a certain amount of gas afterwards, refer to and pass into solvent partial pressure lower than when the gas of front chamber's internal solvent dividing potential drop, to significantly reduce when front chamber's internal solvent dividing potential drop, thus retarder thinner molecular concentration, accelerate solvent evaporation or solvent molecule leaves environment, the solvent vapo(u)r making evaporation quickly leaves the film surface of generation, it is to avoid at liquid film upper strata sustainable existence, solvent vapo(u)r causes that the solvent thin film to generating produces corrosion or solvent ageing behavior。And this gas can not with perovskite generation chemical reaction, in order to avoid causing perovskite thin film to destroy。
Solvent partial pressure in the gas passed in described dry run is less than in current low solvent partial pressure environment the 80% of solvent partial pressure, and being completely dried the solvent partial pressure in the gas passed into afterwards is in current low solvent partial pressure environment the 50%～0 of solvent partial pressure；The flow set of the gas passed into is 0.5-1000 times that evaporates flow in solvent evaporation process, or is ensured to be able to maintain that required ambient pressure under this ventilation flow rate by exhaust capacity decision and exhaust capacity。
Described control drying condition makes matrix surface be crystallization based on out-phase forming core and grow, refer to the control by matrix rough morphology, the speed of evacuation, solution rate of drying and Matrix Solution film thermal are compensated, solution degree of super saturation is made to be not up to homogenous nucleation degree, based on homogenous nucleation in suppression solution, making the preferential out-phase forming core of matrix surface is crystalline growth, and strengthen rate of drying further, make solution internal generation homogenous nucleation and grow, thus accelerating crystallization process, finally grow into the perovskite thin film of dense uniform。Specifically determining of this technological parameter need to obtain, with temperature conditions, the parameter that supersaturation homogenous nucleation is relevant with out-phase forming core for concrete solvent, even if when not having above-mentioned parameter, it is possible to tested by limited number of time and obtain。
In dry run, by the mode of substrate preheating or heating, solution preheating or heating, contactless radiation heating, solution film or matrix are carried out instant heat compensation, to suppress because solution cooling reduces saturated vapor pressure thus affecting rate of drying。
Through the dry perovskite thin film obtained of bleeding, at 57～300 DEG C of temperature, it is carried out 2min～10h heat treatment further, with further optimising and adjustment grainiess, pattern and size。
The method utilizing the venting method of bleeding optimized to prepare perovskite thin film provided by the invention, in dry run of bleeding, as long as making perovskite liquid film keep liquid, namely between freezing point temperature and the boiling temperature of its temperature solute in perovskite liquid film, all can be dried according to the method for the present invention, obtain uniform, fine and close perovskite thin film。Especially, compared with the method for comparative example 4-6, when when drying in the present invention, temperature is lower than 30 DEG C, prepared perovskite thin film has very good performance。
Below in conjunction with comparative example and embodiments of the invention, the present invention is described in further details。Wherein comparative example is divided into 2 groups, comparative example 1-3 adopts and is made directly the mode that heating makes solvent volatilize under normal pressure and prepares perovskite thin film, comparative example 4-6 is by reducing pressure to the saturated vapor pressure of solvent under Current Temperatures, add quick-dissolving agent evaporation, solution is made quickly to have too high saturation, so that a large amount of solutes can on matrix out-phase forming core growing, obtain the perovskite thin film of densification, but do not pass into solvent partial pressure lower than when the gas of solvent partial pressure in environment in dry run or after being completely dried。And embodiments of the invention not only reduce pressure to the saturated vapor pressure of solvent under Current Temperatures, add quick-dissolving agent evaporation, solution is made quickly to have too high saturation, so that a large amount of solutes can on matrix out-phase forming core growing, and in dry run or after being completely dried, pass into solvent partial pressure lower than when in environment solvent partial pressure and not with the gas of perovskite generation chemical reaction, avoid the solvent thin film to generating to produce corrosion or solvent ageing behavior, finally give the perovskite thin film that even structure is fine and close。
Comparative example 1
Step 1) with DMF for solvent, preparation mass percentage concentration is the CH of 35%3NH3PbI3Solution, sprays one layer of CH prepared by nebulization on compliant conductive matrix ITO3NH3PbI3Solution, obtains one layer of perovskite liquid film faint yellow, that thickness is about 1500nm。
Step 2) this perovskite liquid film is placed on the hot plate of 70 DEG C and heats 40min, promote solvent evaporation liquid membrane crystal forming core and grow up, it has been found that its color from light yellow becomes black, obtains one layer of CH3NH3PbI3Thin film, in its pattern such as Fig. 1-1 shown in (a), (b), (c)。
From Fig. 1-1 it can be seen that the CH for preparing of comparative example 13NH3PbI3Thin film is uneven, coarse grains, in dendroid, and the coverage rate of matrix is low。
Comparative example 2
Step 1) with DMSO for solvent, preparation mass percentage concentration is the CH of 35%3NH3PbI3Solution, one layer of CH prepared of blade coating on electro-conductive glass FTO matrix3NH3PbI3Solution, obtains one layer of perovskite liquid film faint yellow, that thickness is about 2000nm。
Step 2) this perovskite liquid film is placed on the hot plate of 200 DEG C heating 30min, make solvent evaporate, liquid film crystallization nucleation growing up on matrix, it has been found that its color from light yellow becomes black, obtains one layer of CH3NH3PbI3Thin film, in its pattern such as Fig. 1-2 shown in (a), (b), (c)。
From Fig. 1-2 it can be seen that the CH for preparing of comparative example 23NH3PbI3Thin film is uneven, coarse grains, in dendroid, and the coverage rate of matrix is low。
Comparative example 3
Step 1) with DMF for solvent, preparation mass percentage concentration is the CH of 40%3NH3PbI3Solution。On electro-conductive glass ITO, one layer of CH prepared is applied by rubbing method3NH3PbI3Solution, obtains one layer of perovskite liquid film faint yellow, that thickness is about 4000nm。
Step 2) this perovskite liquid film is placed on the hot plate of 120 DEG C heating 20min, make solvent evaporate, liquid film heterogeneous crystallization nucleation growing on matrix, while liquid film color from light yellow become black, obtain one layer of CH3NH3PbI3Thin film, in its pattern such as Fig. 1-3 shown in (a), (b), (c)。
From Fig. 1-3 it can be seen that the CH for preparing of comparative example 33NH3PbI3Thin film is uneven, coarse grains, in dendroid, and the coverage rate of matrix is low。
Comparative example 4
1) with DMF for solvent, PbI2And CH3NH3I is solute, prepares perovskite solution, CH in perovskite solution3NH3PbI3Mass percentage concentration be 35%。
2) utilize nebulization to spray one layer of perovskite solution prepared on compliant conductive matrix ITO, obtain one layer of perovskite liquid film faint yellow, that thickness is about 1500nm。
3) carry out bleeding at 50 DEG C dry, at this temperature, the saturated vapor pressure of solvent is about 2200Pa, perovskite liquid film is placed in the chamber of 400Pa, now solvent is 1800Pa with the pressure reduction of chamber pressure, solvent quickly volatilizees, liquid film has high degree of supersaturation, meets the condition of forming core, liquid film out-phase forming core growing on coarse matrix。Solvent volatilizees complete in 30s, is taken out by the thin film obtained after 30s, and thin film color is kermesinus。
4) thin film is placed in heat treatment 15min on the hot plate of 70 DEG C, the CH obtained3NH3PbI3In pattern such as Fig. 2-1 of thin film (perovskite thin film) shown in (a), (b), (c)。
From Fig. 2-1 it can be seen that the CH for preparing of comparative example 43NH3PbI3Thin film is comparatively uniform, fine and close, and the coverage rate of matrix is higher, but there is uniform pores small on a small quantity on the surface that this perovskite thin film still be can be observed under magnification at high multiple multiple。
Comparative example 5
1) with DMSO for solvent, PbI2And CH3NH3I is solute, prepares perovskite solution, CH in perovskite solution3NH3PbI3Mass percentage concentration be 30%。
2) the perovskite solution that blade coating one layer prepares on electro-conductive glass FTO matrix, obtains one layer of perovskite liquid film faint yellow, that thickness is about 2000nm。
3) carrying out bleeding at 70 DEG C dry, at this temperature, the saturated vapor pressure of solvent is about 5900Pa, is placed in the chamber of 40Pa by perovskite liquid film, and now solvent is 5860Pa with the pressure reduction of chamber pressure。After solvent volatilization, liquid film reaches supersaturation, at coarse matrix surface liquid film out-phase forming core and grow。Solvent volatilizees complete in 10s, is taken out by thin film after 10s, and thin film color is kermesinus。
4) thin film is placed in heat treatment 2min on the hot plate of 200 DEG C, the CH obtained3NH3PbI3In film morphology such as Fig. 2-2 shown in (a), (b), (c)。
From Fig. 2-2 it can be seen that the CH for preparing of comparative example 53NH3PbI3Thin film is comparatively uniform, fine and close, and the coverage rate of matrix is higher, but there is more small uniform pores on the surface that this perovskite thin film still be can be observed under magnification at high multiple multiple。
Comparative example 6
1) with DMF for solvent, PbI2And CH3NH3I is solute, prepares perovskite solution, CH in perovskite solution3NH3PbI3Mass percentage concentration be 45%。
2) utilize rubbing method to spray one layer of perovskite solution configured on glass conducting base ITO, obtain one layer of perovskite liquid film faint yellow, that thickness is about 5000nm。
3) carrying out bleeding at 30 DEG C dry, at this temperature, the saturated vapor pressure of solvent is about 740Pa, is placed in the chamber of 600Pa by perovskite liquid film, and now solvent is 140Pa with the pressure reduction of chamber pressure。Solvent quickly volatilizees, and liquid film has high degree of supersaturation, meets the condition of forming core, liquid film out-phase forming core growing on coarse matrix。Solvent volatilizees complete in 60s, is taken out by thin film after 60s, and thin film color is kermesinus。
4) thin film is placed in heat treatment 5min on the hot plate of 120 DEG C, the CH obtained3NH3PbI3In the pattern of thin film such as Fig. 2-3 shown in (a), (b), (c)。
From Fig. 2-3 it can be seen that the CH for preparing of comparative example 63NH3PbI3Thin film is comparatively uniform, fine and close, and the coverage rate of matrix is higher, but under magnification at high multiple multiple, this perovskite thin film still can be observed still have a small amount of extremely small uniform pores。
Embodiment 1
1) with DMF for solvent, PbI2And CH3NH3I is solute, prepares perovskite solution, CH in perovskite solution3NH3PbI3Mass percentage concentration be 35%。
2) utilize nebulization to spray one layer of perovskite solution prepared on compliant conductive matrix ITO, obtain one layer of perovskite liquid film faint yellow, that thickness is about 1500nm。
3) carry out bleeding at 50 DEG C dry, at this temperature, the saturated vapor pressure of solvent is about 2200Pa, perovskite liquid film is placed in the chamber of 400Pa, now solvent is 1800Pa with the pressure reduction of chamber pressure, solvent quickly volatilizees, liquid film has high degree of supersaturation, meets the condition of forming core, liquid film out-phase forming core growing on coarse matrix。In dry run, for avoiding solvent vapo(u)r that thin film is produced corrosion, passing into DMF dividing potential drop in chamber is nearly the air of zero, reduces the dividing potential drop of DMF steam in vacuum chamber, in order to DMF steam is continuing the lower film surface leaving generation in time of bleeding。Continuing chamber to bleed after 1min, taken out by thin film, thin film color is kermesinus。
4) thin film is placed in heat treatment 15min on the hot plate of 70 DEG C, the CH obtained3NH3PbI3In pattern such as Fig. 3-1 of thin film (perovskite thin film) shown in (a), (b), (c)。
From Fig. 3-1 it can be seen that the CH for preparing of embodiment 13NH3PbI3Thin film is visibly homogeneous, fine and close, and the coverage rate of matrix is very high, even and if observing the surface of this perovskite thin film under magnification at high multiple multiple and also occur without any hole。
Embodiment 2
1) with DMSO for solvent, PbI2And CH3NH3I is solute, prepares perovskite solution, CH in perovskite solution3NH3PbI3Mass percentage concentration be 30%。
2) the perovskite solution that blade coating one layer prepares on electro-conductive glass FTO matrix, obtains one layer of perovskite liquid film faint yellow, that thickness is about 2000nm。
3) carrying out bleeding at 70 DEG C dry, at this temperature, the saturated vapor pressure of solvent is about 5900Pa, is placed in the chamber of 40Pa by perovskite liquid film, and now solvent is 5860Pa with the pressure reduction of chamber pressure。After solvent volatilization, liquid film reaches supersaturation, at coarse matrix surface liquid film out-phase forming core and grow。In dry run, for avoiding solvent vapo(u)r that thin film is produced corrosion, in chamber, pass into the nitrogen that DMSO dividing potential drop is about zero, reduce the dividing potential drop of DMSO steam in vacuum chamber, in order to DMSO steam is continuing the lower film surface leaving generation in time of bleeding。Continuing chamber to bleed after 3min, taken out by thin film, thin film color is kermesinus。
4) thin film is placed in heat treatment 2min on the hot plate of 200 DEG C, the CH obtained3NH3PbI3In the pattern of thin film such as Fig. 3-2 shown in (a), (b), (c)。
From Fig. 3-2 it can be seen that the CH for preparing of embodiment 23NH3PbI3Thin film is visibly homogeneous, fine and close, and the coverage rate of matrix is very high, even and if observing the surface of this perovskite thin film under magnification at high multiple multiple and also occur without any hole。
Embodiment 3
1) with DMF for solvent, PbI2And CH3NH3I is solute, prepares perovskite solution, CH in perovskite solution3NH3PbI3Mass percentage concentration be 45%。
2) utilize rubbing method to spray one layer of perovskite solution configured on glass conducting base ITO, obtain one layer of perovskite liquid film faint yellow, that thickness is about 5000nm。
3) carrying out bleeding at 30 DEG C dry, at this temperature, the saturated vapor pressure of solvent is about 740Pa, is placed in the chamber of 600Pa by perovskite liquid film, and now solvent is 140Pa with the pressure reduction of chamber pressure。Solvent quickly volatilizees, and liquid film has high degree of supersaturation, meets the condition of forming core, liquid film out-phase forming core growing on coarse matrix。In dry run, for avoiding solvent vapo(u)r that thin film is produced corrosion, in chamber, pass into the helium that DMF dividing potential drop is close to zero, reduce the dividing potential drop of DMF solvent steam in vacuum chamber, in order to DMF steam is continuing the lower film surface leaving generation in time of bleeding。Continuing chamber to bleed after 8min, taken out by thin film, thin film color is kermesinus。
4) thin film is placed in heat treatment 10min on the hot plate of 100 DEG C, the CH obtained3NH3PbI3In the pattern of thin film such as Fig. 3-3 shown in (a), (b), (c)。
From Fig. 3-3 it can be seen that the CH for preparing of embodiment 33NH3PbI3Thin film is visibly homogeneous, fine and close, and the coverage rate of matrix is very high, even and if observing the surface of this perovskite thin film under magnification at high multiple multiple and also occur without any hole。
By Fig. 1-1,1-2,1-3, Fig. 2-1,2-2,2-3 and Fig. 3-1,3-2,3-3 contrast it can be seen that the perovskite thin film for preparing of traditional heating means is very uneven, coarse grains, in dendroid, the coverage rate of matrix is low。The general method utilizing degassing method to prepare perovskite thin film, although prepared perovskite thin film is comparatively uniform, fine and close, and the coverage rate of matrix is also higher, but still suffers from hole small on a small quantity。And the shortcoming of the thin film that the perovskite thin film utilizing the venting method of bleeding optimized to prepare of the present invention can overcome prior art to prepare, the perovskite thin film of the present invention is visibly homogeneous, fine and close, the coverage rate of matrix is very high, and it is absent from hole, it can be avoided that the current leakage that perovskite thin film leak causes, it is advantageously implemented the manufacture of high performance solar batteries。
Embodiment 4
1) with γ-Ding lactone for solvent, PbBr2And CH3NH3Br is solute, prepares perovskite solution, CH in perovskite solution3NH3PbBr3Mass percentage concentration be 50%。
2) utilize nebulization to spray one layer of perovskite solution prepared on compliant conductive matrix ITO, obtain one layer of perovskite liquid film faint yellow, that thickness is about 1000nm。
3) carry out bleeding at 40 DEG C dry, at this temperature, the saturated vapor pressure of solvent is about 1310Pa, perovskite liquid film is placed in the chamber of 40Pa, now solvent is 1270Pa with the pressure reduction of chamber pressure, solvent quickly volatilizees, liquid film has high degree of supersaturation, meets the condition of forming core, liquid film out-phase forming core growing on coarse matrix。In dry run, for avoiding solvent vapo(u)r that thin film is produced corrosion, γ-Ding lactone dividing potential drop is passed into lower than 70% when the air of the γ-Ding lactone dividing potential drop in front chamber in chamber, reduce the dividing potential drop of γ-Ding lactone steam in vacuum chamber, in order to γ-Ding lactone steam is continuing the lower film surface leaving generation in time of bleeding。Continue chamber to bleed after 15min, thin film is taken out。
4) thin film is placed in heat treatment 30min on the hot plate of 120 DEG C, obtains CH3NH3PbBr3Thin film (perovskite thin film)。
Embodiment 5
1) with DMSO and DMF for solvent, PbCl2And CH3NH3Cl is solute, prepares perovskite solution, CH in perovskite solution3NH3PbCl3Mass percentage concentration be 20%。
2) the perovskite solution that blade coating one layer prepares on electro-conductive glass FTO matrix, obtains one layer of perovskite liquid film faint yellow, that thickness is about 2500nm。
3) carry out bleeding at 60 DEG C dry, at this temperature, the saturated vapor pressure of solvent is about 3700Pa, perovskite liquid film is placed in the chamber of 40Pa, now solvent is 3660Pa with the pressure reduction of chamber pressure, solvent quickly volatilizees, liquid film has high degree of supersaturation, meets the condition of forming core, liquid film out-phase forming core growing on coarse matrix。In dry run, for avoiding solvent vapo(u)r that thin film is produced corrosion, in chamber, pass into solvent partial pressure lower than 30% when the nitrogen of front chamber's internal solvent dividing potential drop, reduce the solvent partial pressure in vacuum chamber, in order to solvent vapo(u)r is continuing the lower film surface leaving generation in time of bleeding。Continue chamber to bleed after 10min, thin film is taken out。
4) thin film is placed in heat treatment 10h on the hot plate of 57 DEG C, obtains CH3NH3PbCl3Thin film。
Embodiment 6
1) with DMF and γ-Ding lactone for solvent, PbI2And CH3NH3Br is solute, prepares perovskite solution, CH in perovskite solution3NH3PbI2The mass percentage concentration of Br is 10%。
2) by rubbing method one layer of perovskite solution prepared of coating on electro-conductive glass ITO matrix, one layer of perovskite liquid film faint yellow, that thickness is about 3000nm is obtained。
3) carry out bleeding at 20 DEG C dry, at this temperature, the saturated vapor pressure of solvent is about 394Pa, perovskite liquid film is placed in the chamber of 40Pa, now solvent is 354Pa with the pressure reduction of chamber pressure, solvent quickly volatilizees, liquid film has high degree of supersaturation, meets the condition of forming core, liquid film out-phase forming core growing on coarse matrix。After being completely dried, for avoiding solvent vapo(u)r that thin film is produced corrosion, passing into solvent partial pressure in chamber is nearly the nitrogen of zero, reduces the dividing potential drop of vacuum chamber internal solvent steam, in order to solvent vapo(u)r is continuing the lower film surface leaving generation in time of bleeding。Continue chamber to bleed after 2min, thin film is taken out。
4) thin film is placed in heat treatment 2min on the hot plate of 300 DEG C, obtains CH3NH3PbI2Br thin film。
Embodiment 7
1) with DMSO and γ-Ding lactone for solvent, PbCl2And CH3NH3I is solute, prepares perovskite solution, CH in perovskite solution3NH3PbCl2The mass percentage concentration of I is 40%。
2) the perovskite solution that blade coating one layer prepares on electro-conductive glass FTO matrix, obtains one layer of perovskite liquid film faint yellow, that thickness is about 3500nm。
3) carry out bleeding at 10 DEG C dry, at this temperature, the saturated vapor pressure of solvent is about 200Pa, perovskite liquid film is placed in the chamber of 10Pa, now solvent is 190Pa with the pressure reduction of chamber pressure, solvent quickly volatilizees, liquid film has high degree of supersaturation, meets the condition of forming core, liquid film out-phase forming core growing on coarse matrix。After being completely dried, for avoiding solvent vapo(u)r that thin film is produced corrosion, in chamber, pass into solvent partial pressure lower than 40% when the air of front chamber's internal solvent dividing potential drop, reduce the solvent partial pressure in vacuum chamber, in order to solvent vapo(u)r is continuing the lower film surface leaving generation in time of bleeding。Continue chamber to bleed after 5min, thin film is taken out。
4) thin film is placed in heat treatment 1h on the hot plate of 100 DEG C, obtains CH3NH3PbCl2I thin film。
Embodiment 8
1) with DMSO and DMF for solvent, PbBr2And CH3NH3Cl is solute, prepares perovskite solution, CH in perovskite solution3NH3PbBr2The mass percentage concentration of Cl is 25%。
2) the perovskite solution that blade coating one layer prepares on electro-conductive glass FTO matrix, obtains one layer of perovskite liquid film faint yellow, that thickness is about 4500nm。
3) carry out bleeding at 25 DEG C dry, at this temperature, the saturated vapor pressure of solvent is about 550Pa, perovskite liquid film is placed in the chamber of 500Pa, now solvent is 50Pa with the pressure reduction of chamber pressure, solvent quickly volatilizees, liquid film has high degree of supersaturation, meets the condition of forming core, liquid film out-phase forming core growing on coarse matrix。In dry run, for avoiding solvent vapo(u)r that thin film is produced corrosion, in chamber, pass into solvent partial pressure lower than 50% when the nitrogen of front chamber's internal solvent dividing potential drop, reduce the solvent partial pressure in vacuum chamber, in order to solvent vapo(u)r is continuing the lower film surface leaving generation in time of bleeding。Continue chamber to bleed after 8min, thin film is taken out。
4) thin film is placed in heat treatment 3min on the hot plate of 250 DEG C, obtains CH3NH3PbBr2Cl thin film。
Claims (10)
1. one kind utilizes solution venting method of bleeding to prepare the method for perovskite thin film in perovskite solaode, it is characterized in that, it concretely comprises the following steps: perovskite solution is coated in matrix surface, form perovskite liquid film, then be placed in low solvent partial pressure environment to carry out bleed dry, when bleeding dry, the temperature of perovskite liquid film is between the freezing point temperature and boiling temperature of solvent, in dry run or be completely dried and pass into gas afterwards, in the way of retarder thinner molecular concentration, accelerate solvent evaporation or solvent molecule leaves this environment, in dry run, control drying condition simultaneously, the solute in perovskite liquid film is made at matrix surface out-phase forming core and to grow, obtain uniformly, fine and close perovskite thin film；Wherein low solvent partial pressure environment refers to that the solvent partial pressure in this environment is lower than solvent saturated vapor pressure of 99% under current baking temperature, solvent partial pressure in the gas passed into is lower than the solvent partial pressure in this environment current, and this gas does not react with perovskite liquid film or thin film, described solvent is the solvent in perovskite solution。
2. according to claim 1 utilize solution venting method of bleeding to prepare the method for perovskite thin film in perovskite solaode, it is characterised in that: the described mixed solvent that the solvent in perovskite solution is one or both arbitrary proportions in DMF, DMSO or γ-Ding lactone；Solute in perovskite solution is mol ratio is the PbX of 1:12And CH3NH3Y, wherein X is I, Br or Cl, and Y is I, Br or Cl, and X and Y is identical or different。
3. according to claim 2 utilize solution venting method of bleeding to prepare the method for perovskite thin film in perovskite solaode, it is characterised in that: PbX in described perovskite solution2And CH3NH3Y shape becomes CH3NH3PbX2Y, CH3NH3PbX2The mass percentage concentration of Y is 10～50%。
4. according to claim 1 utilize solution venting method of bleeding to prepare the method for perovskite thin film in perovskite solaode, it is characterized in that: adopt the mode of blade coating, spraying or coating that perovskite solution is coated in matrix surface, the thickness≤5000nm of the perovskite liquid film obtained。
5. according to claim 1 utilize solution venting method of bleeding to prepare the method for perovskite thin film in perovskite solaode, it is characterised in that: the temperature controlling perovskite solution when bleeding dry is-20～40 DEG C。
6. according to claim 1 utilize solution venting method of bleeding to prepare the method for perovskite thin film in perovskite solaode, it is characterized in that: the solvent partial pressure in the gas passed in dry run is less than in current low solvent partial pressure environment the 80% of solvent partial pressure, and being completely dried the solvent partial pressure in the gas passed into afterwards is in current low solvent partial pressure environment the 50%～0 of solvent partial pressure。
7. according to claim 1 utilize solution venting method of bleeding to prepare the method for perovskite thin film in perovskite solaode, it is characterized in that: control drying condition and make the solute in perovskite liquid film at matrix surface out-phase forming core and grow, refer to by the control to matrix rough morphology, heat compensation, the speed of evacuation and rate of drying, suppress homogenous nucleation in perovskite liquid film, make solute at the preferential out-phase forming core of matrix surface, and continue crystallization, grow into the perovskite thin film of dense uniform。
8. according to claim 7 utilize solution venting method of bleeding to prepare the method for perovskite thin film in perovskite solaode, it is characterised in that: described out-phase forming core, is when the matrix adopting surface smooth, at the uniform out-phase forming core of matrix surface；
Described out-phase forming core, is when adopting coarse matrix, crystalline core size less than matrix rough surface dimple size when, the preferential out-phase forming core at pit position；Or crystalline core size more than matrix rough surface dimple size when, at the uniform out-phase forming core of rough surface。
9. according to claim 7 utilize solution venting method of bleeding to prepare the method for perovskite thin film in perovskite solaode, it is characterised in that: described heat compensation is, by the mode of substrate preheating or heating, the preheating of perovskite liquid film or heating or contactless radiation heating, perovskite liquid film or matrix are carried out instant heat compensation。
10. according to claim 1 utilize solution venting method of bleeding to prepare the method for perovskite thin film in perovskite solaode, it is characterized in that: after bleeding and having dried, the thin film obtained is carried out at 57～300 DEG C the heat treatment of 2min～10h, namely obtains perovskite thin film。
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