CN105826473A - High-efficiency, low-cost perovskite-type solar cell and preparation method for same - Google Patents

Abstract

The invention discloses a high-efficiency, low-cost perovskite-type solar cell which comprises a conducting substrate, an electronic transmission layer, an insulating buffer layer, a perovskite light absorption layer, a hole transport layer and a metal electrode, wherein the perovskite light absorption layer is prepared by a gas-phase auxiliary solution method; and the hole transport layer is a composite layer made of copper acetylacetonate and Spiro-OMeTAD. The invention also discloses a preparation method for the high-efficiency, low-cost perovskite-type solar cell. The perovskite-type solar cell prepared in the invention has the advantages of high photoelectric conversion efficiency, high stability, simple preparation technologies and low cost.

Description

A high-efficiency and low-cost perovskite solar cell and its preparation method

Technical field:

The invention relates to the field of solar cells, in particular to a perovskite solar cell with high efficiency and low cost.

Background technique:

Perovskite solar cells are a new type of solar cells developed on the basis of dye-sensitized solar cells (DSSC). It was first proposed by Japanese scientist Kojima et al. in 2009. Its structure is completely applied to DSSC cells, except that commonly used organic dyes are replaced by CH ₃ NH ₃ PbI ₃ or CH ₃ NH ₃ PbBr ₃ , and its general photoelectric conversion efficiency exceeds 3%. Lead methylamine halide (CH ₃ NH ₃ PbX ₃ ) has a perovskite structure, so this type of solar cell is called a perovskite solar cell. Lead methylamine halides have suitable _bandgap ( _1.5eV for _CH3NH3PbI3 and _2.3eV for _{CH3NH3PbBr3 )} and high light absorption coefficient, accompanied by organic hole The introduction of semiconductor transport materials, especially the use of Spiro-OMeTAD instead of the traditional liquid electrolyte, has greatly improved the photoelectric conversion efficiency of new solar cell devices based on lead methylamine halide materials, thus enabling this type of solar cell to exhibit very The attractive application prospect has become the focus of many researchers and the solar cell industry in recent years.

However, the Spiro-OMeTAD material is expensive and has poor stability, and the perovskite film prepared by the traditional method has many pinholes, large roughness, and poor quality, which seriously affects the photoelectric conversion efficiency of the solar cell, and the perovskite film The interface between the light-absorbing layer and the electron-transporting layer also recombines electrons and holes, which affects the photoelectric performance of solar cells.

Invention content:

The object of the present invention is to provide a high-efficiency and low-cost perovskite solar cell, which has good stability, high photoelectric conversion efficiency and low preparation cost.

Another object of the present invention is to provide a method for preparing the high-efficiency and low-cost perovskite solar cell.

To achieve the above object, the present invention adopts the following technical solutions:

A high-efficiency and low-cost perovskite solar cell, the perovskite solar cell includes a conductive substrate, an electron transport layer, an insulating buffer layer, a perovskite light absorption layer, a hole transport layer, and a metal electrode. The perovskite light absorbing layer is prepared by a gas phase assisted solution method, and the hole transport layer is a composite layer of copper acetylacetonate and Spiro-OMeTAD.

As a preference of the above technical solution, the electron transport layer is a multi-layer structure, including an n-type doped semiconductor oxide layer and an n-type intrinsic semiconductor oxide layer, and the thickness of the n-type doped semiconductor oxide layer is 10-30nm , the thickness of the n-type intrinsic semiconductor oxide layer is 30-50nm.

As a preference of the above technical solution, the n-type intrinsic semiconductor oxide is one of zinc oxide and titanium oxide, and the doping element is one of aluminum, manganese and magnesium.

A method for preparing a high-efficiency and low-cost perovskite solar cell, comprising the following steps:

(1) Soak the conductive substrate with deionized water, acetone and isopropanol solution successively and ultrasonically, and finally dry it with nitrogen and treat it with ultraviolet ozone for 15 minutes, and set it aside;

(2) Spin-coat the n-type doped semiconductor oxide solution on the conductive substrate at a speed of 2000-4000 rpm, anneal at a low temperature of 70-75°C for 10-15min, and then apply the n-type intrinsic semiconductor oxide The solution is spin-coated on the n-type doped semiconductor oxide layer at a speed of 3000-5000 rpm, and annealed at 70-75°C for 15 minutes to obtain an electron transport layer;

(3) Drop the Al ₂ O ₃ precursor solution onto the electron transport layer, let it stand for 30-50s, then spin-coat it at 1000-3000 rpm for 30s, and sinter at 450-500°C for 50-100min , cooled to room temperature to obtain an insulating buffer layer;

(4) Spin-coat the PbX ₂ precursor solution on the insulating buffer layer, then heat it at 80-100°C for 15-30min, and place it in a vacuum drying oven together with iodide powder after natural cooling, at a pressure of 10-20KPa , at a temperature of 150-170°C, heat the iodide powder, evaporate and react with the PbX ₂ film for 50-120min to form a perovskite, wash it with isopropanol after natural cooling, and finally dry it at 150-170°C for 15- 30min, obtain perovskite light absorbing layer;

(5) Spin-coat the acetylacetone precursor solution on the perovskite light-absorbing layer, heat and crystallize at 80-100°C for 20 minutes, cool to room temperature, and then spin-coat 20 μl of Spiro-OMeTAD to obtain a composite hole transport layer;

(6) A metal electrode with a thickness of 60-100 nm is vapor-deposited on the hole transport layer to obtain a high-efficiency and low-cost perovskite solar cell.

As a preferred technical solution, in step (4), the solvent of the PbX ₂ precursor solution is N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, N,N-di One of methyl acetamide, the PbX ₂ concentration in the PbX ₂ precursor solution is 400-500mg/mL.

As a preference of the above technical solution, in step (5), the concentration of the copper acetylacetonate precursor solution is 1.5-3mg/ml, the spin coating speed is 4500r/s, and the time is 30s.

As a preference of the above technical solution, in step (5), the spin coating speed of the Spiro-OMeTAD solution is 4000r/s, and the time is 20s.

As a preference of the above technical solution, in step (3), the solvent of the Al ₂ O ₃ precursor solution is one or a mixture of ethanol and isopropanol, the concentration of which is 10-30 mmol/L.

The present invention has the following beneficial effects:

The present invention adopts n-type doped semiconductor oxide layer and n-type intrinsic semiconductor oxide layer as electron transport layer, and adopts gas phase solution-assisted method to prepare perovskite light absorption layer, and there is oxidation in the middle of light absorption layer and electron transport layer The aluminum insulating buffer layer improves the quality of the perovskite light-absorbing layer, and the photoelectric conversion rate of the prepared perovskite solar cell is greatly improved and the stability is good;

On the other hand, the present invention uses inorganic materials and organic materials as the hole transport layer of solar cells, which has high hole mobility, reduces the recombination of photogenerated carriers, greatly improves the photoelectric performance of solar cells, and its price Inexpensive, greatly increasing the production cost of perovskite solar cells.

detailed description:

In order to better understand the present invention, the present invention will be further described through the following examples, which are only used to explain the present invention and will not constitute any limitation to the present invention.

Example 1

A method for preparing a high-efficiency and low-cost perovskite solar cell, comprising the following steps:

(1) Soak the FTO substrate in deionized water, acetone and isopropanol solution successively and ultrasonically, and finally dry it with nitrogen and treat it with ultraviolet ozone for 15 minutes, and set it aside;

(2) Spin-coat the aluminum-doped zinc oxide solution on the conductive substrate at a speed of 2000 rpm, anneal at a low temperature of 70-75°C for 10 minutes, and then spin-coat the zinc oxide solution on the aluminum alloy at a speed of 3000 rpm. On the magnesium-doped zinc oxide layer, anneal at 70-75°C for 15 minutes to obtain an electron transport layer;

(3) Add the Al ₂ O ₃ precursor solution with a concentration of 10mmol/L onto the electron transport layer dropwise, let it stand for 30s, then spin-coat it at 1000 rpm for 30s, sinter at 450°C for 50min, and cool to room temperature to obtain an insulating buffer layer;

(4) Spin-coat the N,N-dimethylformamide solution of PbCl ₂ with a concentration of 400mg/mL on the insulating buffer layer, then heat at 80°C for 15min, and place it in vacuum together with the iodide powder after natural cooling In the drying box, under the pressure of 10-20KPa and the temperature of 150°C, heat the iodide powder, evaporate and react with the PbCl ₂ film for 50min to form perovskite, clean it with isopropanol after natural cooling, and finally dry it at 150°C Drying for 15 minutes under the hood to obtain a perovskite light-absorbing layer;

(5) Spin-coat an acetylacetone precursor solution with a concentration of 1.5mg/ml on the perovskite light-absorbing layer. The spin-coating speed is 4500r/s, and the time is 30s. Then heat and crystallize at 80°C for 20min, and cool to At room temperature, spin-coat 20 μl of Spiro-OMeTAD at a speed of 4000 r/s for 20 s to obtain a composite hole transport layer;

(6) An Au electrode with a thickness of 60 nm is deposited on the hole transport layer to obtain a high-efficiency and low-cost perovskite solar cell.

Example 2

A method for preparing a high-efficiency and low-cost perovskite solar cell, comprising the following steps:

(1) Soak the FTO substrate in deionized water, acetone and isopropanol solution successively and ultrasonically, and finally dry it with nitrogen and treat it with ultraviolet ozone for 15 minutes, and set it aside;

(2) Spin-coat the solution of manganese mixed with zinc oxide on the conductive substrate at a speed of 4000 rpm, anneal at a low temperature of 70-75 ° C for 15 minutes, and then spin-coat the solution of zinc oxide on the manganese at a speed of 5000 rpm On the doped zinc oxide layer, anneal at 70-75°C for 15 minutes to obtain an electron transport layer;

(3) Add the Al ₂ O ₃ precursor solution with a concentration of 30mmol/L onto the electron transport layer dropwise, let it stand for 50s, then spin-coat it at 3000 rpm for 30s, sinter at 500°C for 100min, and cool to room temperature to obtain an insulating buffer layer;

(4) Spin-coat the N,N-dimethylformamide solution of PbCl ₂ with a concentration of 500mg/mL on the insulating buffer layer, then heat it at 100°C for 30min, and place it in vacuum together with the iodide powder after natural cooling In the drying oven, under the pressure of 10-20KPa and the temperature of 170°C, heat the iodide powder, evaporate and react with the PbCl ₂ film for 120min to form perovskite, clean it with isopropanol after natural cooling, and finally Drying for 30min under the hood to obtain the perovskite light absorbing layer;

(5) Spin-coat an acetylacetone precursor solution with a concentration of 3mg/ml on the perovskite light-absorbing layer. The spin-coating speed is 4500r/s, and the time is 30s. Then heat and crystallize at 100°C for 20min, and cool to room temperature , and then spin-coat 20 μl of Spiro-OMeTAD at a rotating speed of 4000r/s, and the spin-coating time is 20s to obtain a composite hole transport layer;

(6) An Au electrode with a thickness of 100 nm is vapor-deposited on the hole transport layer to obtain a high-efficiency and low-cost perovskite solar cell.

Example 3

A method for preparing a high-efficiency and low-cost perovskite solar cell, comprising the following steps:

(1) Soak the FTO substrate in deionized water, acetone and isopropanol solution successively and ultrasonically, and finally dry it with nitrogen and treat it with ultraviolet ozone for 15 minutes, and set it aside;

(2) Spin-coat the aluminum-magnesium-doped titanium oxide solution on the conductive substrate at a speed of 2500 rpm, anneal at a low temperature of 70-75°C for 11 minutes, and then spin-coat the titanium oxide solution on the conductive substrate at a speed of 3500 rpm. On the aluminum-doped titanium oxide layer, anneal at 70-75°C for 15 minutes to obtain an electron transport layer;

(3) Add the Al ₂ O ₃ precursor solution with a concentration of 15 mmol/L onto the electron transport layer dropwise, let stand for 35 s, then spin-coat at 1500 rpm for 30 s, sinter at 455°C for 60 min, and cool to room temperature to obtain an insulating buffer layer;

(4) Spin-coat the N,N-dimethylformamide solution of PbBr2 with a concentration of _420mg /mL on the insulating buffer layer, then heat it at 85°C for 20min, and place it in vacuum together with iodide powder after natural cooling In the drying oven, under the pressure of 10-20KPa and the temperature of 150°C, heat the iodide powder, evaporate and react with the PbBr ₂ film for 60min to form perovskite, clean it with isopropanol after natural cooling, and finally dry it at 150°C Drying for 20 minutes under the hood to obtain a perovskite light-absorbing layer;

(5) Spin-coat an acetylacetone precursor solution with a concentration of 1.8mg/ml on the perovskite light-absorbing layer. The spin-coating speed is 4500r/s, and the time is 30s. Then heat and crystallize at 85°C for 20min, and cool to At room temperature, spin-coat 20 μl of Spiro-OMeTAD at a speed of 4000 r/s for 20 s to obtain a composite hole transport layer;

(6) An Au electrode with a thickness of 70nm is vapor-deposited on the hole transport layer to obtain a high-efficiency and low-cost perovskite solar cell.

Example 4

A method for preparing a high-efficiency and low-cost perovskite solar cell, comprising the following steps:

(1) Soak the FTO substrate in deionized water, acetone and isopropanol solution successively and ultrasonically, and finally dry it with nitrogen and treat it with ultraviolet ozone for 15 minutes, and set it aside;

(2) Spin-coat the manganese-doped titanium oxide solution on the conductive substrate at a speed of 3000 rpm, anneal at a low temperature of 70-75°C for 12 minutes, and then spin-coat the titanium oxide solution on the manganese at a speed of 4000 rpm. On the doped titanium oxide layer, anneal at 70-75°C for 15 minutes to obtain an electron transport layer;

(3) Add the Al ₂ O ₃ precursor solution with a concentration of 18mmol/L onto the electron transport layer dropwise, let it stand for 40s, then spin-coat it at 2000 rpm for 30s, sinter at 470°C for 70min, and cool to room temperature to obtain an insulating buffer layer;

(4) Spin-coat the dimethyl sulfoxide solution of PbCl2 with a concentration of _4400mg /mL on the insulating buffer layer, then heat it at 90°C for 25min, and place it in a vacuum drying oven together with the iodide powder after natural cooling. At a pressure of 10-20KPa and a temperature of 160°C, heat the iodide powder, evaporate and react with the PbCl ₂ film for 90 minutes to form a perovskite. After natural cooling, clean it with isopropanol, and finally dry it at 160°C for 25 minutes. Obtain a perovskite light absorbing layer;

(5) Spin-coat an acetylacetone precursor solution with a concentration of 2mg/ml on the perovskite light-absorbing layer, spin-coat at a speed of 4500r/s for 30s, then heat and crystallize at 90°C for 20min, and cool to room temperature , and then spin-coat 20 μl of Spiro-OMeTAD at a rotating speed of 4000r/s, and the spin-coating time is 20s to obtain a composite hole transport layer;

(6) An Ag electrode with a thickness of 80nm is vapor-deposited on the hole transport layer to obtain a high-efficiency and low-cost perovskite solar cell.

Example 5

A method for preparing a high-efficiency and low-cost perovskite solar cell, comprising the following steps:

(1) Soak the FTO substrate in deionized water, acetone and isopropanol solution successively and ultrasonically, and finally dry it with nitrogen and treat it with ultraviolet ozone for 15 minutes, and set it aside;

(2) Spin-coat the solution of magnesium mixed with zinc oxide on the conductive substrate at a speed of 3500 rpm, anneal at a low temperature of 70-75 ° C for 13 minutes, and then spin-coat the solution of zinc oxide on the magnesium alloy at a speed of 4000 rpm. On the doped zinc oxide layer, anneal at 70-75°C for 15 minutes to obtain an electron transport layer;

(3) Add the Al ₂ O ₃ precursor solution with a concentration of 25mmol/L onto the electron transport layer dropwise, let it stand for 45s, then spin-coat at 3000 rpm for 30s, sinter at 480°C for 80min, and cool to room temperature to obtain an insulating buffer layer;

(4) spin-coat the gamma-butyrolactone solution of PbCl2 with a concentration of _460mg /mL on the insulating buffer layer, then heat at 95°C for 30min, and place it in a vacuum drying oven together with iodide powder after natural cooling, At a pressure of 10-20KPa and a temperature of 165°C, heat the iodide powder, evaporate and react with a PbCl ₂ film for 100 minutes to form a perovskite. After natural cooling, wash with isopropanol, and finally dry at 165°C for 30 minutes. Obtain a perovskite light absorbing layer;

(5) Spin-coat an acetylacetone precursor solution with a concentration of 2.5mg/ml on the perovskite light-absorbing layer. The spin-coating speed is 4500r/s, and the time is 30s. Then heat and crystallize at 100°C for 20min, and cool to At room temperature, spin-coat 20 μl of Spiro-OMeTAD at a speed of 4000 r/s for 20 s to obtain a composite hole transport layer;

(6) An Ag electrode with a thickness of 90nm is vapor-deposited on the hole transport layer to obtain a high-efficiency and low-cost perovskite solar cell.

Example 6

A method for preparing a high-efficiency and low-cost perovskite solar cell, comprising the following steps:

(1) Soak the FTO substrate in deionized water, acetone and isopropanol solution successively and ultrasonically, and finally dry it with nitrogen and treat it with ultraviolet ozone for 15 minutes, and set it aside;

(2) Spin-coat the solution of magnesium mixed with titanium oxide on the conductive substrate at a speed of 3800 rpm, anneal at a low temperature of 70-75 ° C for 14 minutes, and then spin-coat the solution of titanium oxide on the magnesium alloy at a speed of 4800 rpm. On the doped titanium oxide layer, anneal at 70-75°C for 15 minutes to obtain an electron transport layer;

(3) Add the Al ₂ O ₃ precursor solution with a concentration of 28mmol/L onto the electron transport layer dropwise, let it stand for 50s, then spin-coat it at 2800 rpm for 30s, sinter at 490°C for 90min, and cool to room temperature to obtain an insulating buffer layer;

(4) Spin-coat the N,N-dimethylacetamide solution of _PbI2 with a concentration of 480mg/mL on the insulating buffer layer, then heat at 95°C for 30min, cool naturally and place it in vacuum together with iodide powder In the drying box, under the pressure of 10-20KPa and the temperature of 170°C, heat the iodide powder, evaporate and react with the _PbI2 film for 110min to form perovskite, clean it with isopropanol after natural cooling, and finally dry it at 170°C Drying for 20 minutes under the hood to obtain a perovskite light-absorbing layer;

(5) Spin-coat an acetylacetone precursor solution with a concentration of 2.8mg/ml on the perovskite light-absorbing layer. The spin-coating speed is 4500r/s, and the time is 30s. Then heat and crystallize at 90°C for 20min, and cool to At room temperature, spin-coat 20 μl of Spiro-OMeTAD at a speed of 4000 r/s for 20 s to obtain a composite hole transport layer;

(6) An Ag electrode with a thickness of 95nm is vapor-deposited on the hole transport layer to obtain a high-efficiency and low-cost perovskite solar cell.

Claims (8)

1. a high-efficiency and low-cost Ca-Ti ore type solaode, it is characterised in that this Ca-Ti ore type Solaode include conductive substrates, electron transfer layer, insulating buffer layer, perovskite light absorbing zone, Hole transmission layer, metal electrode, described perovskite light absorbing zone uses gas phase assisted solution method to prepare, Described hole transmission layer is acetylacetone copper and Spiro-OMeTAD composite bed.

2. a kind of high-efficiency and low-cost Ca-Ti ore type solaode as claimed in claim 1, it is special Levying and be, described electron transfer layer is multiple structure, including N-shaped doped semiconductor oxide skin(coating) and n Type intrinsic semiconductor oxide skin(coating), the thickness of N-shaped doped semiconductor oxide skin(coating) is 10-30nm, N-shaped The thickness of intrinsic semiconductor oxide skin(coating) is 30-50nm.

3. a kind of high-efficiency and low-cost Ca-Ti ore type solaode as claimed in claim 2, it is special Levying and be, described N-shaped intrinsic semiconductor oxide is the one in zinc oxide, titanium oxide, described in mix Miscellaneous element is the one in aluminum, manganese, magnesium elements.

4. a kind of high-efficiency and low-cost Ca-Ti ore type solar-electricity as described in claims 1 to 3 is arbitrary The preparation method in pond, it is characterised in that comprise the following steps:

(1) conductive substrates is soaked and ultrasonic with deionized water, acetone and aqueous isopropanol successively, Dry up with nitrogen afterwards and process 15min through UV ozone, stand-by；

(2) by the solution of N-shaped doped semiconductor oxide with the rotating speed spin coating of 2000-4000 rev/min In conductive substrates, 70-75 DEG C of process annealing 10-15min, then by N-shaped intrinsic semiconductor oxide Solution be spun on N-shaped doped semiconductor oxide skin(coating) with the rotating speed of 3000-5000 rev/min, 70-75 DEG C of annealing 15min, obtains electron transfer layer；

(3) by Al₂O₃Precursor solution is added drop-wise on electron transfer layer, stands 30-50s, then exists Spin coating 30s under the state of 1000-3000 rev/min, sinters 50-100min, cooling at 450-500 DEG C To room temperature, obtain insulating buffer layer；

(4) by PbX₂Precursor solution is spin-coated on insulating buffer layer, then heats at 80-100 DEG C 15-30min, is placed in vacuum drying oven after natural cooling together with iodide powder, at pressure is 10-20KPa, at temperature is 150-170 DEG C, heats iodide powder, with PbX after evaporation₂Thin film reacts 50-120min, generates perovskite, is carried out with isopropanol, finally at 150-170 DEG C after natural cooling Under be dried 15-30min, obtain perovskite light absorbing zone；

(5) spin coating acetylacetone,2,4-pentanedione precursor solution on perovskite light absorbing zone, adds at 80-100 DEG C Thermal crystalline 20min, is cooled to room temperature, then the Spiro-OMeTAD of spin coating 20 μ l, obtains compound hole Transport layer；

(6) being deposited with a layer thickness on hole transmission layer is the metal electrode of 60-100nm, obtains height Efficiency low cost Ca-Ti ore type solaode.

The preparation of a kind of high-efficiency and low-cost Ca-Ti ore type solaode the most as claimed in claim 4 Method, it is characterised in that in step (4), described PbX₂The solvent of precursor solution is N, N-diformazan One in base Methanamide, dimethyl sulfoxide, gamma-butyrolacton, N,N-dimethylacetamide, described PbX₂ PbX in precursor solution₂Concentration be 400-500mg/mL.

The preparation of a kind of high-efficiency and low-cost Ca-Ti ore type solaode the most as claimed in claim 4 Method, it is characterised in that in step (5), the concentration of described acetylacetone copper precursor solution is 1.5-3mg/ml, the rotating speed of its spin coating is 4500r/s, and the time is 30s.

The preparation of a kind of high-efficiency and low-cost Ca-Ti ore type solaode the most as claimed in claim 4 Method, it is characterised in that in step (5), the rotating speed of described Spiro-OMeTAD solution spin coating is 4000r/s, the time is 20s.

The preparation of a kind of high-efficiency and low-cost Ca-Ti ore type solaode the most as claimed in claim 4 Method, it is characterised in that in step (3), described Al₂O₃The solvent of precursor solution is ethanol, different One or both mixing in propanol, its concentration is 10-30mmol/L.