Application method of ALD-SnO2 electron transport layer in large-area trans-perovskite assembly

Abstract

The invention provides an application method of an ALD-SnO2 electron transport layer in a large-area trans-perovskite assembly, which comprises the following steps of: 1, performing ultrasonic cleaning on a transparent conductive substrate greater than or equal to 10cm * 10cm by using an alkaline detergent, rinsing by using deionized water, dehydrating by using isopropanol, and performing ultraviolet ozone treatment for 20-30 minutes to remove organic residues; 2, tetrabutyltin and deionized water are used as precursors in an ALD reaction cavity, a SnO2 bottom layer is deposited at 140-180 DEG C, tin source pulse is carried out for 0.8-1.2 s, oxygen source pulse is carried out for 0.3-0.6 s, purge is carried out for 8-12 s, and circulation is carried out 60-90 times till the wavelength is 6-9 nm; 3, trimethylaluminum is introduced, aluminum source pulse is linearly and progressively increased for 0.02-0.1 s to achieve 0.5%-2% gradient doping, and a 3-5 nm layer is formed through 40-70 times of circulation; 4, after oxygen plasma treatment is conducted for 6 min to 12 min, a 0.15 mg / mL to 0.25 mg / mL 2-mercaptopyrimidine ethanol solution is spin-coated, and annealing is conducted for 12 min to 18 min at the temperature ranging from 90 DEG C to 110 DEG C; and step 5, preparing a perovskite layer with the assistance of a gas phase, and sequentially depositing a NiOx electrode and an Ag electrode to complete the assembly. The method solves the problems that the existing ALD-SnO2 is limited in application precursor selection, single in doping strategy and poor in large-area adaptability.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of solar cells, in particular to an application method of an ALD-SnO2 electron transport layer in a large-area inverse perovskite component. BACKGROUND

[0002] SnO2 is an n-type semiconductor metal oxide, which has high electron mobility, wide band gap, good chemical stability and low-temperature processability, and has become a mainstream electron transport layer material for inverse PSCs. Hu Qinghao et al. pointed out in 'Acesulfame-modified SnO2 electron transport layer on the performance of perovskite solar cells' that the high electron mobility of SnO2 can effectively reduce the carrier transport loss, but the oxygen vacancy defects on the surface and grain boundaries will cause serious non-radiative recombination, limiting the improvement of device efficiency.

[0003] Atomic layer deposition (ALD) technology realizes atomic-level precision film growth through the alternation of precursor gas pulses and the use of surface saturation reaction, and has the following advantages: ① excellent thickness uniformity (large-area deviation ≤0.5 nm); ② dense and pore-free film (porosity <0.1%); ③ high controllability of composition (doping concentration deviation ≤0.1%). These characteristics make it an ideal technology for the preparation of large-area electron transport layers.

[0004] However, the existing application of ALD-SnO2 still has the following problems:

[0005] Limited precursor selection: traditional tin tetrachloride (SnCl4) is used as a tin source, and the Cl- residue generated by its hydrolysis will introduce defects and reduce electron mobility;

[0006] Single doping strategy: constant concentration doping is mostly used, which can easily lead to excessive doping of the surface layer, causing lattice distortion, and insufficient doping of the bottom layer, making it difficult to improve the electrical conductivity;

[0007] Lack of surface modification: there are still a large number of oxygen vacancies on the surface of ALD-SnO2, and there is a lack of targeted passivation methods, and the problem of non-radiative recombination is prominent;

[0008] Poor adaptability to large areas: existing processes are mostly aimed at small-area devices (<1cm 2 , without considering the long carrier transport path and large interface stress in large-area components.

[0009] Therefore, it is necessary to provide a new application method of an ALD-SnO2 electron transport layer in a large-area inverse perovskite component to solve the above technical problems. SUMMARY

[0010] To solve the above technical problems, the application provides a method for applying ALD-SnO2 electronic transport layer in large-area reverse perovskite components, which solves the problems of existing ALD-SnO2, such as limited selection of precursors, single doping strategy and poor large-area adaptability.

[0011] The method for applying ALD-SnO2 electronic transport layer in large-area reverse perovskite components provided by the application comprises the following steps:

[0012] Step 1, substrate pretreatment: a transparent conductive substrate with a size of ≥10 cm*10 cm is sequentially subjected to ultrasonic cleaning with an alkaline detergent, rinsing with deionized water, dehydration with isopropanol, and then subjected to ultraviolet ozone treatment for 20-30 min to remove surface organic residues;

[0013] Step 2, ALD-SnO2 bottom layer preparation: the pretreated substrate is placed in an ALD reaction cavity, tetrabutyltin is used as a tin source and deionized water is used as an oxygen source, SnO2 bottom layer is deposited at 140-180°C, the tin source pulse time is 0.8-1.2 s, the oxygen source pulse time is 0.3-0.6 s, the purge time is 8-12 s, the deposition cycle is 60-90 times, and the bottom layer thickness is controlled to be 6-9 nm;

[0014] Step 3, gradient doping layer preparation: the deposition temperature is kept unchanged, trimethylaluminum is introduced as an aluminum source, the linearly increasing aluminum source pulse time (0.02-0.1 s) is used to realize the gradient distribution of Al doping concentration from 0.5% to 2%, the deposition cycle is 40-70 times, and a 3-5 nm gradient doping layer is formed;

[0015] Step 4, surface recombination modification: the deposited substrate is treated in an oxygen plasma for 6-12 min (power 60-100 W, vacuum degree 2-4 Pa), and then a 0.15-0.25 mg / mL 2-mercapto pyrimidine ethanol solution is spin-coated, and annealing is performed at 90-110°C for 12-18 min;

[0016] Step 5, component integration: a perovskite light-absorbing layer is prepared on the modified SnO2 layer by using a gas-phase assisted solution method, NiO x hole transport layer and Ag electrode are sequentially deposited, and large-area reverse perovskite component preparation is completed.

[0017] Preferably, in step 1, the transparent conductive substrate is ITO conductive glass or FTO conductive glass, and the alkaline detergent is a 5% sodium hydroxide solution by mass fraction, and the ultrasonic cleaning time is 25-35 min / time.

[0018] Preferably, after the ultraviolet ozone treatment in step 1, the water contact angle of the surface of the transparent conductive substrate is ≤20°.

[0019] Preferably, the ALD reaction cavity pressure in step 2 is controlled at 100-300 Pa, the carrier gas is nitrogen with a purity of ≥99.999%, and the carrier gas flow is 200-300 sccm.

[0020] Preferably, the pulse time ratio of the aluminum source to the tin source in step 3 is linearly increased with the number of deposition cycles, the initial ratio is 0.02:1, and the final ratio is 0.1:1.

[0021] Preferably, the oxygen plasma treatment in step 4 has an oxygen purity of ≥99.99%, the spin coating rotation speed of the 2-mercapto pyrimidine ethanol solution is 3000-4000 r / min, and the spin coating time is 25-35 s.

[0022] Preferably, the perovskite light-absorbing layer in step 5 is FA0.83Cs 0. 17PbI3system, the film forming temperature of the gas phase assisted solution method is 150-170℃, and the perovskite thin film thickness is 500-600 nm.

[0023] Preferably, the NiO x The hole transport layer is prepared by a magnetron sputtering method, the sputtering power is 100-150 W, the argon / oxygen volume ratio is 3:1, and the thin film thickness is 50-80 nm.

[0024] Preferably, the Ag electrode in step 5 is prepared by a thermal evaporation method, the evaporation rate is 0.5-1 nm / s, the electrode thickness is 100-150 nm, and the active area of the module is 90 cm 2 .

[0025] Preferably, the X-ray diffraction pattern of the SnO2bottom layer in step 2 appears a crystal face characteristic peak at 2θ=26.6°, and the half peak width is ≤0.24°.

[0026] After the surface recombination modification in step 4, the surface roughness (RMS) of the SnO2layer is ≤1.4 nm.

[0027] The beneficial effects of the present application are:

[0028] 1.ALD technology combined with substrate pretreatment, the thickness deviation of the SnO2electron transport layer of a 10cm×10cm module is controlled at ±0.5nm, which is much better than that of the spin coating method (±5nm);The efficiency fluctuation of the module is reduced from >5% to ≤3%, solving the consistency problem of large-area preparation.

[0029] 2.Through the synergistic effect of Al gradient doping and 2-mercapto pyrimidine passivation, the surface oxygen vacancy defect density of SnO2is reduced from 5×10 16 cm -3 to 2×10 16 cm -3; space limited current (SCLC) test shows that the defect density of perovskite layer is reduced from 4.5*10 16 cm -3 to 3.2*10 16 cm -3 , and the non-radiative recombination rate is reduced by 40%.

[0030] 3. AL gradient doping significantly improves the conductivity of SnO2; the surface dipole effect reduces the conduction band offset from 0.45eV to 0.25eV, and the charge extraction efficiency is improved by 25%, and the open circuit voltage (V o c) is increased from 1.08V to 1.15V.

[0031] 3. The photoelectric conversion efficiency of the optimized 10cm*10cm module is 23.2%, among which the short circuit current density is 25.8mA / cm 2 , and the fill factor is 78.3%, which is 19% higher than that of the traditional ALD-SnO2 module (efficiency 19.5%).

[0032] 4. The composite modification layer forms a physical barrier to inhibit the migration of water vapor and ions: after 3000h storage in nitrogen atmosphere, the module efficiency retention rate is 86.5%, which is much higher than that of the unmodified module (65%); after 30d storage in (60±5)% relative humidity, the efficiency still maintains 72% of the initial value, meeting the practical requirements.

[0033] 5. All steps are completed at low temperature (≤180℃), which can be adapted to flexible PET / ITO substrate; ALD process can realize larger area (≥30cm*30cm) module preparation by expanding the reaction cavity, laying a foundation for industrialization. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 The process flow chart of the application method of the ALD-SnO2 electron transport layer provided by the application in a large-area transverse perovskite module;

[0035] Figure 2 It is the first AFM image of the SnO2 electron transport layer in Example 1;

[0036] Figure 3 It is the second AFM image of the SnO2 electron transport layer in Example 1.

[0037] In the figure, the labels are: 1, detection base; 2, supporting arm; 3, mounting plate; 4, adjusting rod; 5, movable plate; 6, movable cylinder; 7, limiting sleeve; 8, scale ruler; 9, first U-shaped frame; 10, first threaded rod; 11, first clamping plate; 12, mounting seat; 13, second U-shaped frame; 14, second threaded rod; 15, second clamping plate; 16, fixed rod; 17, writing board. DETAILED DESCRIPTION

[0038] The application will be further described below in conjunction with the accompanying drawings and embodiments.

[0039] Please refer to Figure 1 and Figure 2 , wherein Figure 1 Process flow diagram of the application method for the application of the ALD-SnO2 electron transport layer in a large-area reverse perovskite component; Figure 2 AFM image of the SnO2 electron transport layer in Example 1; Figure 3 AFM image two of the SnO2 electron transport layer in Example 1.

[0040] In the specific implementation process, as Figures 1-3 shown, the following steps are included:

[0041] Step 1, substrate pretreatment: the transparent conductive substrate with a size of ≥10 cm×10 cm is sequentially subjected to ultrasonic cleaning with an alkaline detergent, rinsing with deionized water, dehydration with isopropanol, and then subjected to ultraviolet ozone treatment for 20-30 min to remove surface organic residues;

[0042] Materials: ITO conductive glass, FTO conductive glass, tetrabutyl tin (99%, Alfa Aesar), trimethylaluminum (98%, Sigma-Aldrich), deionized water (18.2 MΩ·cm), 2-mercapto pyrimidine (98%, Aldrich), ethanol, PbI2, FAI (99.9%, Xi'an Baolai), CsI (99.9%, Xi'an Baolai), DMF (analytical pure, Sigma-Aldrich), DMSO (analytical pure, Sigma-Aldrich), NiO target material (99.9%, Zhongnuo New Material), Ag particles (99.99%, Zhongnuo New Material).

[0043] Instruments: atomic layer deposition system (Beneq TFS200), ultrasonic cleaner (KQ-500DE), ultraviolet ozone cleaner (UV-100), plasma treatment instrument (PX-250), spin coater (KW-4B), vacuum thermal evaporation instrument (JGP-450A), magnetron sputtering instrument (JGP-450A), X-ray diffractometer (XRD, Bruker D8 Advance), atomic force microscope, scanning electron microscope (SEM, ZEISS EVO MA15), X-ray photoelectron spectrometer (XPS, Thermo ESCALAB Xi+), electrochemical workstation (CHI660D), solar simulator (Newport Oriel Sol3A).

[0044] Step 2, ALD-SnO2 bottom layer preparation: the pretreated substrate was placed in the ALD reaction cavity, tetrabutyltin was used as tin source and deionized water was used as oxygen source, SnO2 bottom layer was deposited at 140-180℃, the pulse time of tin source was 0.8-1.2s, the pulse time of oxygen source was 0.3-0.6s, the purge time was 8-12s, the deposition cycle was 60-90 times, and the thickness of the bottom layer was controlled to be 6-9nm;

[0045] Step 3, gradient doped layer preparation: the deposition temperature was kept unchanged, trimethylaluminum was introduced as aluminum source, the pulse time of aluminum source was linearly increased (0.02-0.1s) to realize the gradient distribution of Al doping concentration from 0.5% to 2%, the deposition cycle was 40-70 times, and a 3-5nm gradient doped layer was formed;

[0046] Step 4, surface recombination modification: the deposited substrate was treated in oxygen plasma for 6-12min (power 60-100W, vacuum degree 2-4Pa), and then 0.15-0.25mg / mL 2-mercapto pyrimidine ethanol solution was spin-coated, and annealing was performed at 90-110℃ for 12-18min;

[0047] Step 5, component integration: a perovskite light-absorbing layer was prepared on the modified SnO2 layer by vapor phase assisted solution method, NiO x hole transport layer and Ag electrode were sequentially deposited to complete the preparation of large-area inverse perovskite component.

[0048] The transparent conductive substrate in step 1 was ITO conductive glass or FTO conductive glass, the alkaline detergent was 5% sodium hydroxide solution by mass fraction, and the ultrasonic cleaning time was 25-35min / time.

[0049] After ultraviolet ozone treatment in step 1, the water contact angle of the surface of the transparent conductive substrate was ≤20°.

[0050] In step 2, the pressure in the ALD reaction cavity was controlled to be 100-300Pa, the carrier gas was nitrogen with a purity of ≥99.999%, and the carrier gas flow was 200-300sccm. In step 2, the X-ray diffraction pattern of the SnO2 bottom layer appeared a crystal face characteristic peak at 2θ=26.6°, and the half peak width was ≤0.24°; after surface recombination modification in step 4, the surface roughness (RMS) of the SnO2 layer was ≤1.4nm.

[0051] In step 3, the pulse time ratio of aluminum source to tin source linearly increased with the number of deposition cycles, the initial ratio was 0.02:1, and the final ratio was 0.1:1.

[0052] In step 4, the oxygen plasma treatment used oxygen with a purity of ≥99.99%, the spin-coating speed of 2-mercapto pyrimidine ethanol solution was 3000-4000r / min, and the spin-coating time was 25-35s.

[0053] The perovskite light-absorbing layer in step 5 is FA0.83Cs0.17PbI3 0. 17PbI3system, film-forming temperature of gas-phase assisted solution method is 150-170℃, perovskite film thickness is 500-600nm.

[0054] The NiO in step 5 x The hole transport layer is prepared by magnetron sputtering method, sputtering power is 100-150W, argon-oxygen volume ratio is 3:1, and film thickness is 50-80nm.

[0055] The Ag electrode in step 5 is prepared by thermal evaporation method, evaporation rate is 0.5-1nm / s, electrode thickness is 100-150nm, and active area of the module is 90cm 2 .

[0056] Example 1: Preparation of large-area module based on ITO substrate

[0057] (1) Substrate pretreatment: take 10cm×10cm ITO conductive glass, ultrasonic clean with 5% sodium hydroxide solution, deionized water and isopropanol respectively for 30min, dry with nitrogen after ultraviolet ozone treatment for 25min, and measure the water contact angle as 18°.

[0058] (2) ALD-SnO2 bottom layer preparation: ALD reaction cavity pressure is 200Pa, carrier gas N2 flow is 250sccm, and deposition temperature is 160℃; tetrabutyltin pulse is 1.0s, purge is 10s; deionized water pulse is 0.5s, purge is 10s; deposition cycle is 75 times, 7.5nm thick SnO2 bottom layer is formed, XRD test shows that the characteristic peak of (110) crystal face (2θ=26.6°) has a half peak width of 0.24°, and the crystallinity is good.

[0059] (3) Gradient doped layer preparation: aluminum source pulse time is linearly increased from 0.02s to 0.1s, and the ratio of tin source pulse time is increased from 0.02:1 to 0.1:1; deposition cycle is 55 times, 4nm gradient doped layer is formed, XPS test shows that Al element is uniformly distributed, surface Al concentration is 2%, and bottom layer Al concentration is 0.5%.

[0060] (4) Surface recombination modification: oxygen plasma treatment for 8min (power 80W, vacuum degree 3Pa); configure 0.2mg / mL 2-mercapto pyrimidine ethanol solution, spin coating at 3500r / min for 30s, and annealing at 100℃ for 15min; AFM test shows that the surface roughness (RMS) is reduced from 2.1nm to 1.2nm.

[0061] (5) Device integration: perovskite precursor is 1.5 mol / L PbI2(DMF:DMSO = 9:1), spin-coated and annealed at 160°C for 20 min in FAI / CsI vapor to form 550 nm thick FA0.83Cs 0. 17PbI3thin film, SEM shows uniform grain size (≈1.2 pm); magnetron sputtering of NiO x (thickness 60 nm), thermal evaporation of Ag electrode (thickness 120 nm), active area of device 90 cm 2 .

[0062] Example 2: Large-area device fabrication based on FTO substrate

[0063] (1) Substrate pretreatment: take 10 cm x 10 cm FTO conductive glass, clean the process as in Example 1, ultraviolet ozone treatment for 30 min, water contact angle 16°.

[0064] (2) ALD-Sn02underlayer preparation: deposition temperature 140°C, tetrabutyltin pulse 0.8 s, deionized water pulse 0.3 s, purge time 8 s, deposition cycle 60 times, underlayer thickness 6 nm.

[0065] (3) Gradient doped layer preparation: aluminum source pulse time from 0.02 s to 0.08 s, deposition cycle 40 times, form 3 nm doped layer, surface Al concentration 1.5%.

[0066] (4) Surface recombination modification: oxygen plasma treatment for 6 min (power 60 W), spin-coat 0.15 mg / mL 2-mercapto pyrimidine solution (3000 r / min, 25 s), 90°C annealing for 12 min, RMS roughness 1.4 nm.

[0067] (5) Device integration: perovskite film forming temperature 150°C, NiO x thickness 50 nm, Ag electrode thickness 100 nm, active area of device 90 cm 2 .

[0068] Example 3: Comparative experiment (unmodified ALD-Sn02device)

[0069] Except for step 3 using constant Al doping (concentration 1%) and step 4 not performing plasma treatment and organic passivation, the rest of the steps are the same as Example 1, serving as a control group.

[0070] (1) Thin film performance test

[0071] XRD analysis: The SnO2 electron transport layer of Example 1 has a strong diffraction peak at 26.6°, corresponding to the (110) crystal plane of SnO2, indicating that the thin film is well crystallized; the control group has a half-peak width of 0.28° due to constant doping, and the crystallinity is reduced.

[0072] AFM analysis: The SnO2 surface RMS of Example 1 is 1.2 nm, and the control group is 2.1 nm, indicating that the composite modification effectively reduces the roughness.

[0073] XPS analysis: In the O1s spectrum of Example 1, the proportion of lattice oxygen (530.5 eV) increased from 72% to 85%, and the proportion of oxygen vacancies (531.6 eV) decreased from 28% to 15%, indicating significant defect passivation effect.

[0074] Conductivity test: Using the four-probe method, the conductivity of SnO2 in Example 1 is 8×10 -6 S / cm, and the control group is 4.2×10 -6 S / cm, indicating that gradient doping significantly improves the conductivity.

[0075] (2) Component photoelectric performance test

[0076] Test the J-V curve of the component under AM1.5G light (100 mW / cm 2 ):

[0077] Example 1: V o c=1.15 V, J s c=25.8 mA / cm 2 , FF=78.3%, PCE=23.2%;

[0078] Example 2: V o c=1.13 V, J s c=25.2 mA / cm 2 , FF=77.5%, PCE=22.5%;

[0079] Control group: V o c=1.08 V, J s c=23.5 mA / cm 2 , FF=72.1%, PCE=19.5%.

[0080] External quantum efficiency (EQE) test shows that the integrated current of Example 1 in the wavelength range of 300-750 nm is 25.2 mA / cm 2 , which is consistent with the J-V test results, verifying the reliability of the data.

[0081] (3) Stability test

[0082] Nitrogen atmosphere storage: PCE retention rate of 86.5% for the Example 1 module after 3000h storage in a nitrogen glovebox, compared to 65% for the control;

[0083] Humidity stability: PCE retention rate of 72% for the Example 1 module after 30d at (60±5)% RH at room temperature, compared to 45% for the control;

[0084] Light stability: PCE retention rate of 75% for the Example 1 module after 1000h continuous AM1.5G light exposure (without encapsulation), compared to 50% for the control.

[0085] (4) Large-area uniformity test

[0086] A 10cm x 10cm module prepared according to Example 1 was subjected to a 9-point scan (3x3 array), with efficiencies ranging from 22.5% to 23.2% and a deviation of <3%, indicating excellent large-area uniformity.

[0087] The circuits and controls involved in the present application are all prior art and will not be described in detail here.

[0088] The above only describes the embodiments of the present application, and does not limit the patent scope of the present application. Any equivalent structure or equivalent process transformation using the content of the present application specification and drawings, or direct or indirect application in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A method for applying an ALD-SnO2 electron transport layer in a large-area inverse perovskite module, characterized in that, Includes the following steps: Step 1, Substrate Pretreatment: Transparent conductive substrates with dimensions ≥10cm×10cm are sequentially ultrasonically cleaned with alkaline detergent, rinsed with deionized water, dehydrated with isopropanol, and then treated with ultraviolet ozone for 20-30 minutes to remove organic residues on the surface. Step 2, ALD-SnO2 underlayer preparation: The pretreated substrate is placed in the ALD reaction chamber, and a SnO2 underlayer is deposited at 140-180℃ using tetrabutyltin as the tin source and deionized water as the oxygen source. The tin source pulse time is 0.8-1.2s, the oxygen source pulse time is 0.3-0.6s, the purge time is 8-12s, the deposition cycle is 60-90 times, and the underlayer thickness is controlled to be 6-9nm. Step 3, Gradient doping layer preparation: Keeping the deposition temperature constant, trimethylaluminum is introduced as the aluminum source. By linearly increasing the aluminum source pulse time (0.02-0.1s), a gradient distribution of Al doping concentration from 0.5% to 2% is achieved. The deposition cycle is 40-70 times to form a 3-5nm gradient doping layer. Step 4, Surface composite modification: The deposited substrate is treated in oxygen plasma for 6-12 min (power 60-100W, vacuum degree 2-4Pa), and then spin-coated with 0.15-0.25 mg / mL of 2-mercaptopyrimidine ethanol solution and annealed at 90-110℃ for 12-18 min. Step 5, Component Integration: A perovskite light-absorbing layer is prepared on the modified SnO2 layer using a vapor-assisted solution method, followed by the sequential deposition of NiO. x Hole transport layer and Ag electrode were used to complete the fabrication of a large-area inverse perovskite module.

2. The method for applying the ALD-SnO2 electron transport layer in a large-area inverse perovskite module according to claim 1, characterized in that, In step 1, the transparent conductive substrate is ITO conductive glass or FTO conductive glass, the alkaline detergent is a 5% sodium hydroxide solution, and the ultrasonic cleaning time is 25-35 min / cycle.

3. The method for applying the ALD-SnO2 electron transport layer in a large-area inverse perovskite module according to claim 1, characterized in that, After ultraviolet ozone treatment in step 1, the water contact angle on the surface of the transparent conductive substrate is ≤20°.

4. The method for applying the ALD-SnO2 electron transport layer in a large-area inverse perovskite module according to claim 1, characterized in that, In step 2, the pressure in the ALD reaction chamber is controlled at 100-300 Pa, the carrier gas is nitrogen with a purity of ≥99.999%, and the carrier gas flow rate is 200-300 sccm.

5. The method for applying the ALD-SnO2 electron transport layer in a large-area inverse perovskite module according to claim 1, characterized in that, In step 3, the pulse time ratio of the aluminum source to the tin source increases linearly with the number of deposition cycles, with an initial ratio of 0.02:1 and a final ratio of 0.1:

1.

6. The method for applying the ALD-SnO2 electron transport layer in a large-area inverse perovskite module according to claim 1, characterized in that, In step 4, the oxygen purity of the oxygen plasma treatment is ≥99.99%, the spin coating speed of the 2-mercaptopyrimidine ethanol solution is 3000-4000 r / min, and the spin coating time is 25-35 s.

7. The method for applying the ALD-SnO2 electron transport layer in a large-area inverse perovskite module according to claim 1, characterized in that, In step 5, the perovskite light-absorbing layer is FA0.83Cs.

0. For the 17PbI3 system, the film formation temperature using the vapor-assisted solution method is 150-170℃, and the perovskite film thickness is 500-600nm.

8. The method for applying the ALD-SnO2 electron transport layer in a large-area inverse perovskite module according to claim 1, characterized in that, NiO in step 5 x The hole transport layer was prepared by magnetron sputtering with a sputtering power of 100-150W, an argon-oxygen volume ratio of 3:1, and a film thickness of 50-80nm.

9. The method for applying the ALD-SnO2 electron transport layer in a large-area inverse perovskite module according to claim 1, characterized in that, In step 5, the Ag electrode is prepared by thermal evaporation at a rate of 0.5-1 nm / s, with an electrode thickness of 100-150 nm and an active area of ​​90 cm². 2 .

10. The method for applying the ALD-SnO2 electron transport layer in a large-area inverse perovskite module according to claim 1, characterized in that, In step 2, the X-ray diffraction pattern of the SnO2 bottom layer shows a characteristic peak of the crystal plane at 2θ = 26.6°, with a full width at half maximum (FWHM) ≤ 0.24°. After surface composite modification in step 4, the surface roughness (RMS) of the SnO2 layer is ≤1.4nm.

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