CN109802043A - Nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer and preparation method thereof - Google Patents
Nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of nitrogen sulphur codope graphene quantum dot perovskite light-absorption layers and preparation method thereof, belong to technical field of solar batteries.Contain nitrogen sulphur codope graphene quantum dot in the perovskite light-absorption layer of nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer of the invention, the nitrogen sulphur codope graphene quantum dot is the graphene quantum dot for being doped with nitrogen and sulphur；The doping 0.1%~5.0% of nitrogen in the nitrogen sulphur codope graphene quantum dot；The doping 1.0%~10.0% of sulphur.The present invention mixes nitrogen sulphur codope graphene quantum dot in perovskite light-absorption layer for the first time, has the advantage that a. has slowed down perovskite crystalline process, to increase crystallite dimension；B. nitrogen sulphur codope graphene quantum dot can also be passivated trap states by the interaction of Pb cation and iodide ion with coordination；C. it and is introduced into nitrogen sulphur codope graphene quantum dot and is conducive to separation of charge and transfer in perovskite thin film.
Description
Technical field
The present invention relates to a kind of nitrogen sulphur codope graphene quantum dot perovskite light-absorption layers and preparation method thereof, belong to the sun
It can battery technology field.
Background technique
Perovskite solar cell is using the organic metal halide semiconductor of Ca-Ti ore type as the sun of light absorbent
Energy battery, belongs to third generation solar cell, and the structure of perovskite solar cell generally comprises the (plating of substrate material/electro-conductive glass
Have the substrate glass of oxide skin(coating))/electron transfer layer (titanium dioxide)/perovskite light-absorption layer (hole transmission layer)/metallic cathode.
Since the 21th century, environmental pollution and energy crisis are increasingly sharpened, and are developed and are utilized new cleaning fuel technology
It is extremely urgent.Solar battery is concerned due to having the outstanding advantages such as cleaning, efficient, renewable, and accounts for the principal status of public economy
Silicon solar cell higher cost, and high, pollution of consuming energy during the production of high-purity silicon material, silicon ingot melting, silicon wafer cutting etc.
Weight, therefore hinder the paces of silicon solar cell marketization application.Development and production are environmentally friendly, low in cost, incident photon-to-electron conversion efficiency
High solar battery becomes the common recognition of industry.Due to perovskite material abundant raw material, photoelectric properties it is superior, it is low in cost, can
The advantages of solution is processed has obtained extensive research in area of solar cell, and the halide perovskite sun is blended in organic/inorganic
Energy battery also has become the hot spot direction of photovoltaic cell research.
Currently, with TiO2For the perovskite solar battery of electron transport material, due to TiO2The photoinduction of surface adsorbed oxygen
Desorption, it is poor in long-term illumination (including ultraviolet light) stability inferior.And due in perovskite volatile organic component and
Ion transfer, when working at high temperature, serious degradation can occur for perovskite solar battery.In addition, Au atom from electrode to
Calcium titanium ore bed diffusion, and influence another key factor of cell degradation.
Based on the above issues, in order to realize that society is served in the commercialization of perovskite solar battery as early as possible, calcium is being solved
While stability problem caused by titanium ore itself, selects appropriate charge transport layer and metal electrode is perovskite solar battery
The ideal method of business application.
Progress electronic component and material of the such as Wang Jun grapheme material in perovskite solar battery
.2017.6.vol.36No.6 one layer of graphene quantum dot of painting, photoelectric conversion between calcium titanium ore bed and electron transfer layer are disclosed
Efficiency is up to 10.15%；Short-circuit current density 17.06mA/cm2.Still it is not able to satisfy commercialization demand.
Summary of the invention
The invention solves first problem be to provide a kind of nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer.
In order to solve the first technical problem mentioned above, nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer of the invention exists
Contain nitrogen sulphur codope graphene quantum dot in perovskite light-absorption layer, the nitrogen sulphur codope graphene quantum dot is to be doped with nitrogen
With the graphene quantum dot of sulphur；
The doping 0.1%~5.0% of nitrogen in the nitrogen sulphur codope graphene quantum dot；The doping 1.0% of sulphur~
10.0%；
PbI in the nitrogen sulphur codope graphene quantum dot and perovskite light-absorption layer2Mass ratio is preferably 0.02~
0.06:624~1872；PbI in nitrogen sulphur codope graphene quantum dot and perovskite2Mass ratio be more preferably: 0.02~
0.03:624~748.
Preferably, the preparation method of the nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer includes:
I: nitrogen sulphur codope graphene quantum dot, graphene quantum dot and anhydrous n,N-Dimethylformamide being mixed, surpassed
1~3h of sound obtains solution A, the nitrogen sulphur codope graphene quantum dot, graphene quantum dot and anhydrous n,N-Dimethylformamide
Mass ratio are as follows: 0.02~0.06:0.02~0.06:945~2835；Preferred mass ratio are as follows: 0.02~0.03:0.02~0.03:
945~1089；
II: by CH3NH3I and PbI2It is dissolved in solution A and being uniformly mixed, obtain CH3NH3PbI3Precursor solution, it is described
CH3NH3I、PbI2With the mass ratio of solution A are as follows: 0.216~0.648:0.624~1.872:0.945~2.835, the mixing
Uniformly 60~90min of preferred stirring；
III: by CH3NH3PbI3Precursor solution is spin-coated on α-Fe2O3On layer, immediately 105~120 DEG C heat 10~
30min is up to nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer；
The spin coating is preferably by 80~100 μ LCH3NH3PbI3Precursor solution applies rotation 30 with 5000~8000rpm revolving speed
180~300 μ L anhydrous chlorobenzenes are dripped to rapidly coating surface in spin coating process by~60s.
Preferably, the preparation method of the nitrogen sulphur codope graphene quantum dot includes:
Thiocarbamide is completely dissolved in aqueous citric acid solution and obtains mixture；By mixture 160~200 DEG C react 8~
10h obtains transparent blue solution；Dry blue solution removes after water removal 12~15h of dialysis again, obtains nitrogen sulphur codope graphene
Quantum dot；
Wherein, the concentration of the aqueous citric acid solution is 16.8~50.4g/L, and the concentration of optimization citric acid aqueous solution is
16.8~17.8g/L；The mass ratio of the aqueous citric acid solution and thiocarbamide are as follows: 26.26~78.78:1.37~4.11；It is preferred that institute
State the mass ratio of aqueous citric acid solution and thiocarbamide are as follows: 26.26~27.16:1.37~1.56；It is also preferable to include by nitrogen sulphur codope
Graphene quantum dot is dry, removal of impurities obtains nitrogen sulphur codope graphene quantum dot powder.
Preferably, the drying is vacuum drying；The removal of impurities are as follows: second is added in nitrogen sulphur codope graphene quantum dot
Alcohol, 20~40min of ultrasound obtain uniform nitrogen sulphur codope graphene quantum dot suspension, by suspension centrifugation, freeze-drying
Obtain nitrogen sulphur codope graphene quantum dot powder；
The centrifugation is preferably centrifuged 15~30min with the revolving speed of 9000~12000rpm.
Preferably, the preparation method of the graphene quantum dot includes:
NaOH is dissolved in 11.21g/L~100.92g/L aqueous citric acid solution, then 160~200 DEG C react 8~
10h obtains clear solution；Clear solution is removed to 12~15h of dialysis after extra water, obtains graphene quantum dot, the lemon
Lemon aqueous acid and NaOH mass ratio are 25.841~77.523:0.48~1.44；
It is also preferable to include graphene quantum dot is dry, removal of impurities to obtain graphene quantum dot powder；
The drying is vacuum drying, the removal of impurities are as follows: it is added ethyl alcohol in graphene quantum dot, 20~40min of ultrasound,
Uniform graphene quantum dot suspension is obtained, centrifugation, freeze-drying obtain graphene quantum dot powder；
The centrifugation is preferably centrifuged 15~30min with the revolving speed of 10000rpm.
The invention solves second technical problem be to provide a kind of nitrogen sulphur codope graphene quantum dot perovskite too
Positive energy battery.
In order to solve second technical problem of the invention, the light-absorption layer of perovskite solar battery of the invention is above-mentioned
Nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer.
Preferably, the electron transfer layer of the perovskite solar battery is α-Fe2O3；
The preparation method of the preferred electron transfer layer includes: by 0.1~3mol Fe (NO3)3·9H2O is dissolved in second
In alcohol, with 6000~9000rpm revolving speed on substrate 40~60s of spin coating, then in 450~500 DEG C of 1~2h of sintering, obtain densification
α-Fe2O3Coating.
Preferably, one layer of graphene amount is inserted between the calcium titanium ore bed and hole transmission layer of the perovskite solar battery
Son point layer；
The preferred graphene quantum dot layer the preparation method comprises the following steps: by 5mg mL-1The chlorobenzene solution of graphene quantum dot
It drips on calcium titanium ore bed, with 5000~8000rpm revolving speed 60~90s of spin coating, glass culture dish covering and in culture dish edge drop
Upper 8~12 μ l (3- mercaptopropyi) trimethoxy silane, 105~120 DEG C of 60~90min of heating.
The invention solves third technical problem be to provide a kind of nitrogen sulphur codope graphene quantum dot perovskite and inhale
The preparation method of photosphere.
In order to solve third technical problem of the invention, the preparation side of nitrogen sulphur codope graphene quantum dot of the invention
Method includes:
I: nitrogen sulphur codope graphene quantum dot, graphene quantum dot and anhydrous n,N-Dimethylformamide being mixed, surpassed
1~3h of sound obtains solution A, the nitrogen sulphur codope graphene quantum dot, graphene quantum dot and anhydrous n,N-Dimethylformamide
Mass ratio are as follows: 0.02~0.06:0.02~0.06:945~2835；Preferred mass ratio are as follows: 0.02~0.03:0.02~0.03:
945~1089；
II: by CH3NH3I and PbI2It is dissolved in solution A and being uniformly mixed, obtain CH3NH3PbI3Precursor solution, it is described
CH3NH3I、PbI2With the mass ratio of solution A are as follows: 0.216~0.648:0.624~1.872:0.945~2.835, the mixing
Uniformly 60~90min of preferred stirring；
III: by CH3NH3PbI3Precursor solution is spin-coated on α-Fe2O3On layer, immediately 105~120 DEG C heat 10~
30min is up to nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer；
The spin coating is preferably by 80~100 μ L CH3NH3PbI3Precursor solution is applied with 5000~8000rpm revolving speed to be revolved
180~300 μ L anhydrous chlorobenzenes are dripped to rapidly coating surface in spin coating process by 30~60s.
Preferably, the preparation method of the nitrogen sulphur codope graphene quantum dot includes:
Thiocarbamide is completely dissolved in aqueous citric acid solution and obtains mixture；By mixture 160~200 DEG C react 8~
10h obtains transparent blue solution；Dry blue solution removes after water removal 12~15h of dialysis again, obtains nitrogen sulphur codope graphene
Quantum dot；
Wherein, the concentration of the aqueous citric acid solution is 16.8~50.4g/L, and the concentration of optimization citric acid aqueous solution is
16.8~17.8g/L；The mass ratio of the aqueous citric acid solution and thiocarbamide are as follows: 26.26~78.78:1.37~4.11；It is preferred that institute
State the mass ratio of aqueous citric acid solution and thiocarbamide are as follows: 26.26~27.16:1.37~1.56；It is also preferable to include by nitrogen sulphur codope
Graphene quantum dot is dry, removal of impurities obtains nitrogen sulphur codope graphene quantum dot powder；
The preparation method of the graphene quantum dot includes:
NaOH is dissolved in 11.21g/L~100.92g/L aqueous citric acid solution, then 160~200 DEG C react 8~
10h obtains clear solution；Clear solution is removed to 12~15h of dialysis after extra water, obtains graphene quantum dot, the lemon
Lemon aqueous acid and NaOH mass ratio are 25.841~77.523:0.48~1.44；
It is also preferable to include graphene quantum dot is dry, removal of impurities to obtain graphene quantum dot powder；
The drying is vacuum drying, the removal of impurities are as follows: it is added ethyl alcohol in graphene quantum dot, 20~40min of ultrasound,
Uniform graphene quantum dot suspension is obtained, centrifugation, freeze-drying obtain graphene quantum dot powder；
The centrifugation is preferably centrifuged 15~30min with the revolving speed of 10000rpm.
The utility model has the advantages that
(1), the present invention mixes nitrogen sulphur codope graphene quantum dot (NSGQDs) in perovskite light-absorption layer for the first time, has
Following advantage:
A. perovskite crystalline process has been slowed down, to increase crystallite dimension；
B. nitrogen sulphur codope graphene quantum dot (NSGQDs) can also pass through the Pb cation and iodide ion with coordination
Interaction is to be passivated trap states；
C. it and is introduced into nitrogen sulphur codope graphene quantum dot (NSGQDs) and is conducive to separation of charge in perovskite thin film
And transfer.
(2), nitrogen sulphur codope graphene quantum dot (NSGQDs) of the invention and graphene quantum dot (GQDs) are all made of
Hydration method preparation, simple process and synthesis cost is lower are conducive to the commercial applications of perovskite solar battery.
(3), Ca-Ti ore type of the invention α-Fe used for solar batteries2O3Substitute TiO2As electron transfer layer, with the present invention
Nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer match the performance for further increasing perovskite solar battery.
(4), Ca-Ti ore type solar battery of the invention is inserted into one layer of graphite between calcium titanium ore bed and hole transmission layer
Alkene quantum dot, to protect perovskite from moisture attack.
(5), the incident photon-to-electron conversion efficiency of perovskite solar cell of the invention is high.
(6), under continuous illumination, including ultraviolet light, especially under high-intensity ultraviolet light, nitrogen sulphur codope graphene amount
Sub- point NSGQDs perovskite solar cell shows excellent photostability.
Specific embodiment
The preparation method of nitrogen sulphur codope graphene quantum dot (NSGQDs) perovskite solar cell mainly includes that nitrogen sulphur is total
The preparation of doped graphene quantum dot (NSGQDs), graphene quantum dot (GQDs) and solar battery, wherein solar battery
Preparation process include the preparation of FTO substrate, α-Fe2O3The preparation of electron transfer layer, nitrogen sulphur codope graphene quantum dot
(NSGQDs) preparation of calcium titanium ore bed, the preparation of graphene quantum dot (GQDs) layer, the preparation of hole transmission layer and gold electrode
Preparation.
The preparation of one, nitrogen sulphur codope graphene quantum dot (NSGQDs)
1.26~3.78g citric acid is weighed to be dissolved in the deionized water of 25~75mL, while stirring ultrasound 15~
30min dissolves citric acid sufficiently；1.37~4.11g thiocarbamide is weighed to be dissolved in mixed liquor, while stirring ultrasound 15~
45min dissolves thiocarbamide sufficiently；Mixture is put into 100mL using Teflon to seal in the stainless steel autoclave of liner,
8~10h is reacted in 160~200 DEG C of baking ovens, obtains transparent blue solution；Vacuum drying blue solution removes extra water, will
Mixture is put into 12~15h of dialysis in dialysis bag, and the nitrogen sulphur codope graphene quantum dot (NSGQDs) in dialysis bag is taken to be put into
It is dry in vacuum oven to remove extra water；Nitrogen sulphur codope graphene quantum dot (NSGQDs) is added in ethyl alcohol, ultrasound
20~40min obtains uniform nitrogen sulphur codope graphene quantum dot (NSGQDs) suspension, is centrifuged with the revolving speed of 10000rpm
15~30min, centrifugation product are freeze-dried to obtain nitrogen sulphur codope graphene quantum dot (NSGQDs) powder.
The preparation of two, graphene quantum dots (GQDs)
0.841~2.523g citric acid is weighed to be dissolved in the deionized water of 25~75mL, while stirring ultrasound 15~
30min dissolves citric acid sufficiently；0.48~1.44g NaOH is weighed to be dissolved in mixed liquor, while stirring ultrasound 15~
30min dissolves NaOH sufficiently；Mixture is put into 50mL using Teflon to seal in the stainless steel autoclave of liner, 160
8~10h is reacted in~200 DEG C of baking ovens, obtains clear solution；Vacuum drying clear solution removes extra water, and mixture is put
Enter 12~15h of dialysis in dialysis bag, the graphene quantum dot (GQDs) in dialysis bag is taken to be put into vacuum oven dry removal
Extra water；Graphene quantum dot (GQDs) is added in ethyl alcohol, 20~40min of ultrasound obtains uniform graphene quantum dot
(GQDs) suspension is centrifuged 15~30min with the revolving speed of 10000rpm, and centrifugation product is freeze-dried to obtain graphene quantum dot
(GQDs) powder.
The preparation of three, nitrogen sulphur codope graphene quantum dot (NSGQDs) perovskite solar cells
Step 1: the preparation of FTO substrate
Zinc powder and HCl etch FTO coated glass substrate (about 7~15 Ω sq of sheet resistance-1) required electrode shape is obtained,
Detergent (2%Hellmanex aqueous solution), distilled water, ethyl alcohol, acetone and isopropanol 20~40min of ultrasonic cleaning are successively used,
15~30min is cleaned under the conditions of UV-ozone；
Step 2: α-Fe2O3The preparation of electron transfer layer
By 0.1~3mol Fe (NO3)3·9H2O is dissolved in ethyl alcohol, with 6000~9000rpm revolving speed in clean FTO
40~60s of spin coating on coated glass substrate is sintered 1~2h at a temperature of 450~500 DEG C in air, obtains fine and close α-Fe2O3
Coating；
Step 3: the preparation of nitrogen sulphur codope graphene quantum dot (NSGQDs) calcium titanium ore bed
I: weighing 0.02~0.06mg nitrogen sulphur codope graphene quantum dot (NSGQDs) and 0.02~0.06mg graphene
Quantum dot (GQDs) is added in the anhydrous n,N-Dimethylformamide of 1~3mL (DMF), 1~3h of ultrasound；
II: weighing 0.216~0.648g CH3NH3I and 0.624~1.872g PbI2It is dissolved in step 3: the solution of I preparation
In, 60~90min is stirred at room temperature and obtains CH3NH3PbI3Precursor solution；
III: in nitrogen charging glove box, with spin coating on 5000~8000rpm revolving speed α-Fe2O3 coating obtained in step 2
The CH of 80~100 μ L step IIs preparation3NH3PbI330~60s of precursor solution, 180~300 μ L anhydrous chlorobenzenes in spin coating process
Coating surface is dripped to rapidly, and the film of preparation heats 10~30min in 105~120 DEG C of heating plate immediately；
Step 4: the preparation of graphene quantum dot (GQDs) layer
By 5mg mL-1Graphene quantum dot (GQDs) chlorobenzene solution drips to the perovskite-based on piece of step III preparation, with
5000~8000rpm revolving speed 60~90s of spin coating, glass culture dish cover and drip upper 8~12 μ l (3- sulfydryl third at culture dish edge
Base) trimethoxy silane (Sigma-Aldrich), 60~90min is heated in 105~120 DEG C of heating plates；
Step 5: the preparation of hole transmission layer
IV: weighing 72.3~144.6mg 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell two
Fluorenes (spiro-OMeTAD) measures 28.8~57.6 μ L4- tert .-butylpyridines (TBP) and the bis- fluoroform sulphonyl of 17.5~35 μ L
Imine lithium (LiTFSI) solution, which is added in 1~2mL chlorobenzene, is prepared into spiro-OMeTAD solution；
V: after the film cooling to room temperature of step 4 preparation, the spin coating on calcium titanium ore bed with 4000~5000rpm revolving speed
Spiro-OMeTAD 40~50s of solution is formed hole mobile material (HTM), and dry 12~15h in drying box；
Step 6: the preparation of gold electrode
Weigh the spun gold that 0.03g purity is 99.999%, by way of vacuum thermal evaporation on the hole transport layer, deposition
With a thickness of the gold electrode of 100nm.
A specific embodiment of the invention is further described below with reference to embodiment, is not therefore limited the present invention
System is among the embodiment described range.
Embodiment 1
The preparation of one, nitrogen sulphur codope graphene quantum dot (NSGQDs)
It weighs 1.26g citric acid to be dissolved in the deionized water of 25mL, ultrasound 15min, keeps citric acid abundant while stirring
Dissolution；It weighs 1.37g thiocarbamide to be dissolved in mixed liquor, ultrasound 15min, dissolves thiocarbamide sufficiently while stirring；Mixture is put
Enter 50mL using Teflon to seal in the stainless steel autoclave of liner, react 8h in 160 DEG C of baking ovens, it is molten to obtain transparent blue
Liquid；Vacuum drying blue solution removes extra water, and mixture is put into dialysis 12h in dialysis bag, takes the nitrogen sulphur in dialysis bag
Codope graphene quantum dot (NSGQDs) is put into the water that dry removal is extra in vacuum oven；By nitrogen sulphur codope graphene
Quantum dot (NSGQDs) is added in ethyl alcohol, ultrasonic 20min, and it is outstanding to obtain uniform nitrogen sulphur codope graphene quantum dot (NSGQDs)
Supernatant liquid is centrifuged 15min with the revolving speed of 10000rpm, and centrifugation product is freeze-dried to obtain nitrogen sulphur codope graphene quantum dot
(NSGQDs) powder detects the doping 2.6% of nitrogen in nitrogen sulphur codope graphene quantum dot；The doping 5.2% of sulphur.
The preparation of two, graphene quantum dots (GQDs)
It weighs 0.841g citric acid to be dissolved in the deionized water of 25mL, ultrasound 15min, keeps citric acid abundant while stirring
Dissolution；It weighs 0.48g NaOH to be dissolved in mixed liquor, ultrasound 15min, dissolves NaOH sufficiently while stirring；Mixture is put
Enter 50mL using Teflon to seal in the stainless steel autoclave of liner, reacts 8h in 160 DEG C of baking ovens, obtain clear solution；Very
The dry clear solution of sky removes extra water, and mixture is put into dialysis 12h in dialysis bag, takes the graphene quantum in dialysis bag
Point (GQDs) is put into the water that dry removal is extra in vacuum oven；Graphene quantum dot (GQDs) is added in ethyl alcohol, ultrasound
20min obtains uniform graphene quantum dot (GQDs) suspension, is centrifuged 15min with the revolving speed of 10000rpm, centrifugation product is cold
Jelly is dried to obtain graphene quantum dot (GQDs) powder.
The preparation of three, nitrogen sulphur codope graphene quantum dot (NSGQDs) perovskite solar cells
Step 1: zinc powder and HCl etch FTO coated glass substrate (about 15 Ω sq of sheet resistance-1) obtain required electrode
Shape is successively respectively washed with detergent (2%Hellmanex aqueous solution), distilled water, ethyl alcohol, acetone and isopropanol ultrasonic wave
20min cleans 15min under the conditions of UV-ozone；
Step 2: by 0.1mol Fe (NO3)3·9H2O is dissolved in ethyl alcohol, with 6000rpm revolving speed after step 1 cleaning
FTO coated glass substrate on spin coating 40s, be sintered 1h at a temperature of 450 DEG C in air, obtain fine and close α-Fe2O3Coating；
Step 3: 0.02mg nitrogen sulphur codope graphene quantum dot (NSGQDs) and 0.02mg graphene quantum dot are weighed
(GQDs), it is added in the anhydrous n,N-Dimethylformamide of 1mL (DMF), ultrasonic 1h；
Step 4: 0.216g CH is weighed3NH3I and 0.624g PbI2It is dissolved in the solution of step 3 preparation, at room temperature
Stirring 60min obtains CH3NH3PbI3Precursor solution；
Step 5: in nitrogen charging glove box, with 5000rpm revolving speed α-Fe obtained in step 22O380 μ L of spin coating on coating
The CH of step 4 preparation3NH3PbI3Precursor solution 30s, 180 μ L anhydrous chlorobenzenes drip to rapidly coating surface in spin coating process, make
Standby film heats 10min in 105 DEG C of heating plate immediately；
Step 6: by 5mg mL-1Graphene quantum dot (GQDs) chlorobenzene solution drips to the perovskite substrate of step 5 preparation
On, with 5000rpm revolving speed spin coating 60s, glass culture dish covers and drips upper 8-12 μ l (3- mercaptopropyi) three at culture dish edge
Methoxy silane (Sigma-Aldrich) heats 60min in 105 DEG C of heating plates；
Step 7: 72.3mg 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, two fluorenes is weighed
(spiro-OMeTAD), 28.8 μ L 4- tert .-butylpyridines (TBP) and the bis- trifluoromethanesulfonimide lithiums of 17.5 μ L are measured
(LiTFSI) solution, which is added in 1mL chlorobenzene, is prepared into spiro-OMeTAD solution；
Step 8: after the film cooling to room temperature of step 6 preparation, the spin coating on calcium titanium ore bed with 4000rpm revolving speed
Spiro-OMeTAD solution 40s is formed hole mobile material (HTM), and the dry 12h in drying box；
Step 9: the spun gold that 0.03g purity is 99.999% is weighed, in hole transmission layer by way of vacuum thermal evaporation
On, deposition thickness is the gold electrode of 100nm.
Light is carried out to nitrogen sulphur codope graphene quantum dot (NSGQDs) perovskite solar cell that embodiment 1 is prepared
Electric performance test, the anti-incident photon-to-electron conversion efficiency PCE swept are 17.5%, open-circuit voltage VOCFor 999mV, short-circuit current density JSCFor
23.84mA cm-2, fill factor FF is 75.0%.After the battery places 1200h under the environmental condition of 50 ± 10%RH, light
Electrotransformation efficiency PCE still has the 85% of starting efficiency, and after general perovskite battery places 600h under the same conditions, photoelectricity
Transfer efficiency PCE is almost reduced to 0.
After the battery is placed 1200 hours in the drier of low relative humidity (10 ± 5%RH), incident photon-to-electron conversion efficiency
PCE still has the 96% of starting efficiency, and the incident photon-to-electron conversion efficiency PCE of general perovskite battery at this time only has starting efficiency
65%.
In addition, nitrogen sulphur codope graphene quantum dot (NSGQDs) perovskite solar cell of the invention is black in 85 DEG C of constant temperature
After dark condition places 300h, incident photon-to-electron conversion efficiency still has the 93% of starting efficiency, and general perovskite solar battery
Have already decreased to the 45% of starting efficiency.
As it can be seen that nitrogen sulphur codope graphene quantum dot (NSGQDs) perovskite solar cell light with higher of the invention
Electrotransformation efficiency and excellent photostability, comprehensive performance are excellent.
Claims (10)
1. nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer, which is characterized in that contain nitrogen sulphur in perovskite light-absorption layer
Codope graphene quantum dot, the nitrogen sulphur codope graphene quantum dot is the graphene quantum dot for being doped with nitrogen and sulphur；
The doping 0.1%~5.0% of nitrogen in the nitrogen sulphur codope graphene quantum dot；The doping 1.0% of sulphur~
10.0%；
PbI in the nitrogen sulphur codope graphene quantum dot and perovskite light-absorption layer2Mass ratio is preferably 0.02~0.06:624
~1872；PbI in nitrogen sulphur codope graphene quantum dot and perovskite2Mass ratio be more preferably: 0.02~0.03:624
~748.
2. nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer according to claim 1, which is characterized in that the nitrogen
The preparation method of sulphur codope graphene quantum dot perovskite light-absorption layer includes:
I: nitrogen sulphur codope graphene quantum dot, graphene quantum dot and anhydrous n,N-Dimethylformamide are mixed, ultrasound 1~
3h obtains solution A, the nitrogen sulphur codope graphene quantum dot, graphene quantum dot and anhydrous n,N-Dimethylformamide mass ratio
Are as follows: 0.02~0.06:0.02~0.06:945~2835；Preferred mass ratio are as follows: 0.02~0.03:0.02~0.03:945~
1089；
II: by CH3NH3I and PbI2It is dissolved in solution A and being uniformly mixed, obtain CH3NH3PbI3Precursor solution, the CH3NH3I、
PbI2With the mass ratio of solution A are as follows: 0.216~0.648:0.624~1.872:0.945~2.835, it is described to be uniformly mixed preferably
Stir 60~90min；
III: by CH3NH3PbI3Precursor solution is spin-coated on α-Fe2O3On layer, it is in 105~120 DEG C of 10~30min of heating immediately
Obtain nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer；
The spin coating is preferably by 80~100 μ LCH3NH3PbI3Precursor solution with 5000~8000rpm revolving speed apply rotation 30~
180~300 μ L anhydrous chlorobenzenes are dripped to rapidly coating surface in spin coating process by 60s.
3. nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer according to claim 1 or 2, which is characterized in that institute
The preparation method for stating nitrogen sulphur codope graphene quantum dot includes:
Thiocarbamide is completely dissolved in aqueous citric acid solution and obtains mixture；By mixture in 160~200 DEG C of 8~10h of reaction,
Obtain transparent blue solution；Dry blue solution removes after water removal 12~15h of dialysis again, obtains nitrogen sulphur codope graphene quantum
Point；
Wherein, the concentration of the aqueous citric acid solution is 16.8~50.4g/L, the concentration of optimization citric acid aqueous solution is 16.8~
17.8g/L；The mass ratio of the aqueous citric acid solution and thiocarbamide are as follows: 26.26~78.78:1.37~4.11；It is preferred that the lemon
The mass ratio of aqueous acid and thiocarbamide are as follows: 26.26~27.16:1.37~1.56；It is also preferable to include by nitrogen sulphur codope graphene
Quantum dot is dry, removal of impurities obtains nitrogen sulphur codope graphene quantum dot powder.
4. nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer according to claim 3, which is characterized in that described dry
Dry is vacuum drying；The removal of impurities are as follows: ethyl alcohol is added in nitrogen sulphur codope graphene quantum dot, 20~40min of ultrasound is obtained
Suspension centrifugation, freeze-drying are obtained nitrogen sulphur codope graphene by uniform nitrogen sulphur codope graphene quantum dot suspension
Quantum dot powder；
The centrifugation is preferably centrifuged 15~30min with the revolving speed of 9000~12000rpm.
5. according to the described in any item nitrogen sulphur codope graphene quantum dot perovskite light-absorption layers of claim 2~4, feature exists
In the preparation method of the graphene quantum dot includes:
NaOH is dissolved in 11.21g/L~100.92g/L aqueous citric acid solution, then in 160~200 DEG C of 8~10h of reaction, is obtained
To clear solution；Clear solution is removed to 12~15h of dialysis after extra water, obtains graphene quantum dot, the citric acid water
Solution and NaOH mass ratio are 25.841~77.523:0.48~1.44；
It is also preferable to include graphene quantum dot is dry, removal of impurities to obtain graphene quantum dot powder；
The drying is vacuum drying, the removal of impurities are as follows: ethyl alcohol is added in graphene quantum dot, 20~40min of ultrasound is obtained
Uniform graphene quantum dot suspension, centrifugation, freeze-drying obtain graphene quantum dot powder；
The centrifugation is preferably centrifuged 15~30min with the revolving speed of 10000rpm.
6. nitrogen sulphur codope graphene quantum dot perovskite solar battery, which is characterized in that the perovskite solar battery
Light-absorption layer be the described in any item nitrogen sulphur codope graphene quantum dot perovskite light-absorption layers of Claims 1 to 5.
7. nitrogen sulphur codope graphene quantum dot perovskite solar battery according to claim 6, which is characterized in that institute
The electron transfer layer for stating perovskite solar battery is α-Fe2O3；
The preparation method of the electron transfer layer includes: by 0.1~3mol Fe (NO3)3·9H2O is dissolved in ethyl alcohol, with 6000
~9000rpm revolving speed 40~60s of spin coating on substrate, then in 450~500 DEG C of 1~2h of sintering, obtain fine and close α-Fe2O3It applies
Layer.
8. nitrogen sulphur codope graphene quantum dot perovskite solar battery according to claim 6 or 7, feature exist
In one layer of graphene quantum dot layer of insertion between the calcium titanium ore bed and hole transmission layer of the perovskite solar battery；
The preferred graphene quantum dot layer the preparation method comprises the following steps: by 5mg mL-1The chlorobenzene solution of graphene quantum dot drips to
On calcium titanium ore bed, with 5000~8000rpm revolving speed 60~90s of spin coating, glass culture dish covering and culture dish edge drop it is upper 8~
12 μ l (3- mercaptopropyi) trimethoxy silane, 105~120 DEG C of 60~90min of heating.
9. the preparation method of nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer, which is characterized in that the nitrogen sulphur codope
The preparation method of graphene quantum dot includes:
I: nitrogen sulphur codope graphene quantum dot, graphene quantum dot and anhydrous n,N-Dimethylformamide are mixed, ultrasound 1~
3h obtains solution A, the nitrogen sulphur codope graphene quantum dot, graphene quantum dot and anhydrous n,N-Dimethylformamide mass ratio
Are as follows: 0.02~0.06:0.02~0.06:945~2835；Preferred mass ratio are as follows: 0.02~0.03:0.02~0.03:945~
1089；
II: by CH3NH3I and PbI2It is dissolved in solution A and being uniformly mixed, obtain CH3NH3PbI3Precursor solution, the CH3NH3I、
PbI2With the mass ratio of solution A are as follows: 0.216~0.648:0.624~1.872:0.945~2.835, it is described to be uniformly mixed preferably
Stir 60~90min；
III: by CH3NH3PbI3Precursor solution is spin-coated on α-Fe2O3On layer, it is in 105~120 DEG C of 10~30min of heating immediately
Obtain nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer；
The spin coating is preferably by 80~100 μ LCH3NH3PbI3Precursor solution with 5000~8000rpm revolving speed apply rotation 30~
180~300 μ L anhydrous chlorobenzenes are dripped to rapidly coating surface in spin coating process by 60s.
10. the preparation method of nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer according to claim 9, feature
It is, the preparation method of the nitrogen sulphur codope graphene quantum dot includes:
Thiocarbamide is completely dissolved in aqueous citric acid solution and obtains mixture；By mixture in 160~200 DEG C of 8~10h of reaction,
Obtain transparent blue solution；Dry blue solution removes after water removal 12~15h of dialysis again, obtains nitrogen sulphur codope graphene quantum
Point；
Wherein, the concentration of the aqueous citric acid solution is 16.8~50.4g/L, the concentration of optimization citric acid aqueous solution is 16.8~
17.8g/L；The mass ratio of the aqueous citric acid solution and thiocarbamide are as follows: 26.26~78.78:1.37~4.11；It is preferred that the lemon
The mass ratio of aqueous acid and thiocarbamide are as follows: 26.26~27.16:1.37~1.56；It is also preferable to include by nitrogen sulphur codope graphene
Quantum dot is dry, removal of impurities obtains nitrogen sulphur codope graphene quantum dot powder；
The preparation method of the graphene quantum dot includes:
NaOH is dissolved in 11.21g/L~100.92g/L aqueous citric acid solution, then in 160~200 DEG C of 8~10h of reaction, is obtained
To clear solution；Clear solution is removed to 12~15h of dialysis after extra water, obtains graphene quantum dot, the citric acid water
Solution and NaOH mass ratio are 25.841~77.523:0.48~1.44；
It is also preferable to include graphene quantum dot is dry, removal of impurities to obtain graphene quantum dot powder；
The drying is vacuum drying, the removal of impurities are as follows: ethyl alcohol is added in graphene quantum dot, 20~40min of ultrasound is obtained
Uniform graphene quantum dot suspension, centrifugation, freeze-drying obtain graphene quantum dot powder；
The centrifugation is preferably centrifuged 15~30min with the revolving speed of 10000rpm.
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