CN110931641A - Silicon-based organic-inorganic hybrid solar cell and preparation method thereof - Google Patents
Silicon-based organic-inorganic hybrid solar cell and preparation method thereof Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 77
- 239000010703 silicon Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 93
- 239000000758 substrate Substances 0.000 claims abstract description 92
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 claims abstract description 67
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 24
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims abstract description 18
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 60
- 238000004528 spin coating Methods 0.000 claims description 30
- 238000000137 annealing Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000002207 thermal evaporation Methods 0.000 claims description 12
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 238000005566 electron beam evaporation Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 6
- 230000001035 methylating effect Effects 0.000 claims description 6
- 239000002070 nanowire Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000001039 wet etching Methods 0.000 claims description 5
- 238000001312 dry etching Methods 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920001940 conductive polymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention relates to a silicon-based organic-inorganic hybrid solar cell and a preparation method thereof, and the silicon-based organic-inorganic hybrid solar cell comprises the following steps: preparing a silicon wire array on the upper surface of an N-type monocrystalline silicon substrate, and then passivating the N-type monocrystalline silicon substrate; preparing a first Spiro-OMeTAD layer, a second Spiro-OMeTAD layer and a first PEDOT under certain pressure, and then preparing a front electrode on the N-type monocrystalline silicon substrate; evaporating a lithium fluoride layer on the back surface of the N-type monocrystalline silicon substrate; and preparing a back electrode on the back of the N-type monocrystalline silicon substrate.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a silicon-based organic-inorganic hybrid solar cell and a preparation method thereof.
Background
Compared with the traditional monocrystalline silicon battery or polycrystalline silicon battery, the schottky solar battery based on the transparent conducting layer and the silicon has the advantages of simple structure, simple and easy preparation process and no need of high-temperature process in the preparation process, thereby arousing the interest of researchers in colleges and universities and enterprises. In recent years, conductive polymers such as Spiro-OMeTAD, P3HT, PEDOT: PSS and the like are widely applied to silicon-based organic-inorganic hybrid solar cells due to high electrical conductivity and high light transmittance. However, in the process of preparing the conductive polymer layer on the surface of the silicon wire, since the silicon wire has a very high specific surface area, the quality of the conductive polymer layer becomes a key factor influencing the photoelectric conversion efficiency of the conductive polymer layer, and how to prepare the high-quality conductive polymer layer is a research hotspot of researchers.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a silicon-based organic-inorganic hybrid solar cell and a preparation method thereof.
In order to achieve the purpose, the preparation method of the silicon-based organic-inorganic hybrid solar cell provided by the invention comprises the following steps:
1) providing an N-type monocrystalline silicon substrate, and preparing a silicon wire array on the upper surface of the N-type monocrystalline silicon substrate, wherein the length of a silicon wire in the silicon wire array is 2-5 microns, the diameter of the silicon wire is 600-900 nanometers, and the distance between adjacent silicon nanowires is 1-2 microns;
2) then passivating the N-type monocrystalline silicon substrate;
3) preparation of the first Spiro-OMeTAD layer: at a pressure of 1.0X 105In a closed cavity Pa, dripping a first Spiro-OMeTAD solution on the N-type monocrystalline silicon substrate obtained in the step 2, standing for 1-2 minutes, and keeping the pressure in the closed cavity from 1.0 multiplied by 10 in the standing process5Pa is gradually increased to 1.3X 105Pa, then at a pressure of 1.3X 105Spin-coating for 60-90 seconds under the Pa condition, and then carrying out first annealing treatment to form a first Spiro-OMeTAD layer;
4) preparation of a second spiral-OMeTAD layer: at a pressure of 1.3X 105In a closed cavity Pa, dripping a second Spiro-OMeTAD solution on the N-type monocrystalline silicon substrate obtained in the step 3, standing for 1-2 minutes, and keeping the pressure in the closed cavity from 1.3 multiplied by 10 in the standing process5Pa is gradually increased to 1.6X 105Pa, then at a pressure of 1.6X 105Spin-coating for 60-90 seconds under the Pa condition, and then carrying out second annealing treatment to form a second Spiro-OMeTAD layer;
5) preparation of the first PEDOT: PSS layer: at a pressure of 1.0X 105In a closed cavity of Pa, dripping the PEDOT/PSS solution on the N-type monocrystalline silicon substrate obtained in the step 4, standing for 1-2 minutes, and keeping the pressure in the closed cavity from 1.0 multiplied by 10 in the standing process5Pa is gradually increased to 1.5X 105Pa, then at a pressure of 1.5X 105Spin-coating for 60-90 seconds under the Pa condition, and then carrying out third annealing treatment to form a first PEDOT (PSS) layer;
6) preparing a front electrode on the N-type monocrystalline silicon substrate obtained in the step 5;
7) evaporating a lithium fluoride layer on the back surface of the N-type monocrystalline silicon substrate obtained in the step 6;
8) and (4) preparing a back electrode on the back of the N-type monocrystalline silicon substrate obtained in the step (7).
Preferably, in the step 1, the silicon line array is prepared on the upper surface of the N-type monocrystalline silicon substrate by wet etching or dry etching.
Preferably, in the step 2), the step of passivating the N-type monocrystalline silicon substrate includes: soaking the N-type monocrystalline silicon substrate in HF for 3-10 minutes, then chlorinating the hydrogenated N-type monocrystalline silicon substrate to change a silicon-hydrogen bond into a silicon-chlorine bond, and then methylating the N-type monocrystalline silicon substrate to change the silicon-chlorine bond into a silicon-carbon bond to passivate the N-type monocrystalline silicon substrate.
Preferably, in the step 3), the concentration of the Spiro-OMeTAD in the first Spiro-OMeTAD solution is 10-20mg/ml, the rotation speed of the first Spiro-OMeTAD solution in the spin coating process is 2000-3000 r/min, and the specific steps of the first annealing process are as follows: at a pressure of 1.3X 105Heat treatment is carried out for 10-15 minutes under the condition of Pa and the temperature of 80-90 ℃.
Preferably, in the step 4), the concentration of the Spiro-OMeTAD in the second Spiro-OMeTAD solution is 5-10mg/ml, the rotation speed of spin-coating the second Spiro-OMeTAD solution is 3000-: at a pressure of 1.6X 105Heat treatment is carried out for 15-20 minutes under the condition of Pa and the temperature of 85-95 ℃.
Preferably, in the step 5), the rotation speed of the spin coating of the PEDOT: PSS solution is 2500-: at a pressure of 1.5X 105Heat treatment is carried out for 20-30 minutes under the condition of Pa and the temperature of 120-140 ℃.
Preferably, in the step 6), the method for forming the front electrode is one of thermal evaporation, magnetron sputtering and electron beam evaporation, the material of the front electrode is copper or silver, the thickness of the front electrode is 90-150 nm, and the front electrode is a gate electrode.
Preferably, in the step 7), the thickness of the lithium fluoride layer is 1-2 nm, and in the step 8), the method for forming the back electrode is one of thermal evaporation, magnetron sputtering and electron beam evaporation, the material of the back electrode is aluminum, and the thickness of the back electrode is 100-200 nm.
The invention also provides a silicon-based organic-inorganic hybrid solar cell which is prepared by adopting the method.
Compared with the prior art, the invention has the following advantages:
preparing a first Spiro-OMeTAD layer, a second Spiro-OMeTAD layer and a first PEDOT on a silicon wire array: in the course of the PSS layer, by increasing the pressure of the closed cavity during standing, the ratio of the Spiro-OMeTAD solution to the PEDOT: the PSS solution more readily enters the gaps between adjacent silicon lines in the array of silicon lines, meanwhile, a certain pressure is kept in the closed cavity in the processes of spin coating and annealing, so that the pressure of the vortex-OMeTAD and the PEDOT: PSS is more easily attached to the silicon wire, and then a first compact spiral-OMeTAD layer, a second compact spiral-OMeTAD layer and a first PEDOT: a layer of PSS, meanwhile, the filling factor and the short-circuit current of the silicon-based organic-inorganic hybrid solar cell are effectively improved by optimizing the type and the layer number of the conductive polymer and further optimizing the concentration and the annealing process of each Spiro-OMeTAD solution, and the photoelectric conversion efficiency of the silicon-based organic-inorganic hybrid solar cell is further improved.
Drawings
Fig. 1 is a schematic structural diagram of a silicon-based organic-inorganic hybrid solar cell according to the present invention.
Detailed Description
The invention specifically provides a preparation method of a silicon-based organic-inorganic hybrid solar cell, which comprises the following steps:
1) providing an N-type monocrystalline silicon substrate, preparing a silicon wire array on the upper surface of the N-type monocrystalline silicon substrate, wherein the length of a silicon wire in the silicon wire array is 2-5 micrometers, the diameter of the silicon wire is 600-900 nanometers, the distance between adjacent silicon nanowires is 1-2 micrometers, and in the step 1, preparing the silicon wire array on the upper surface of the N-type monocrystalline silicon substrate through wet etching or dry etching.
2) And then passivating the N-type monocrystalline silicon substrate, wherein the specific steps of passivating the N-type monocrystalline silicon substrate are as follows: soaking the N-type monocrystalline silicon substrate in HF for 3-10 minutes, then chlorinating the hydrogenated N-type monocrystalline silicon substrate to change a silicon-hydrogen bond into a silicon-chlorine bond, and then methylating the N-type monocrystalline silicon substrate to change the silicon-chlorine bond into a silicon-carbon bond to passivate the N-type monocrystalline silicon substrate.
3) Preparation of the first Spiro-OMeTAD layer: at a pressure of 1.0X 105In a closed cavity Pa, dripping a first Spiro-OMeTAD solution on the N-type monocrystalline silicon substrate obtained in the step 2, standing for 1-2 minutes, and keeping the pressure in the closed cavity from 1.0 multiplied by 10 in the standing process5Pa is gradually increased to 1.3X 105Pa, then at a pressure of 1.3X 105Spin coating for 60-90 seconds under the condition of Pa, and then carrying out first annealing treatment to form a first Spiro-OMeTAD layer.
In the step 3), the concentration of the Spiro-OMeTAD in the first Spiro-OMeTAD solution is 10-20mg/ml, the rotation speed of the first Spiro-OMeTAD solution in the spin coating process is 2000-3000 r/min, and the specific steps of the first annealing process are as follows: at a pressure of 1.3X 105Heat treatment is carried out for 10-15 minutes under the condition of Pa and the temperature of 80-90 ℃.
4) Preparation of a second spiral-OMeTAD layer: at a pressure of 1.3X 105In a closed cavity Pa, dripping a second Spiro-OMeTAD solution on the N-type monocrystalline silicon substrate obtained in the step 3, standing for 1-2 minutes, and keeping the pressure in the closed cavity from 1.3 multiplied by 10 in the standing process5Pa is gradually increased to 1.6X 105Pa, then at a pressure of 1.6X 105And (4) spin-coating for 60-90 seconds under the Pa condition, and then carrying out second annealing treatment to form a second Spiro-OMeTAD layer.
In the step 4), the concentration of the Spiro-OMeTAD in the second Spiro-OMeTAD solution is 5-10mg/ml, the rotation speed of the second Spiro-OMeTAD solution in the spin coating process is 3000-: at a pressure of 1.6X 105At 85-95 ℃ under the condition of PaHeat treatment for 15-20 minutes under the condition of (1).
5) Preparation of the first PEDOT: PSS layer: at a pressure of 1.0X 105In a closed cavity of Pa, dripping the PEDOT/PSS solution on the N-type monocrystalline silicon substrate obtained in the step 4, standing for 1-2 minutes, and keeping the pressure in the closed cavity from 1.0 multiplied by 10 in the standing process5Pa is gradually increased to 1.5X 105Pa, then at a pressure of 1.5X 105Spin coating for 60-90 seconds under the Pa condition, and then carrying out third annealing treatment to form a first PEDOT (PSS) layer.
Wherein, in the step 5), the rotation speed of the spin coating of the PEDOT/PSS solution is 2500-: at a pressure of 1.5X 105Heat treatment is carried out for 20-30 minutes under the condition of Pa and the temperature of 120-140 ℃.
6) Preparing a front electrode on the N-type monocrystalline silicon substrate obtained in the step 5, wherein the method for forming the front electrode is one of thermal evaporation, magnetron sputtering and electron beam evaporation, the front electrode is made of copper or silver, the thickness of the front electrode is 90-150 nanometers, and the front electrode is a gate electrode.
7) And (6) evaporating a lithium fluoride layer on the back surface of the N-type monocrystalline silicon substrate obtained in the step (6), wherein the thickness of the lithium fluoride layer is 1-2 nanometers.
8) And (3) preparing a back electrode on the back of the N-type monocrystalline silicon substrate obtained in the step (7), wherein the method for forming the back electrode is one of thermal evaporation, magnetron sputtering and electron beam evaporation, the material of the back electrode is aluminum, and the thickness of the back electrode is 100-200 nm.
The invention also provides a silicon-based organic-inorganic hybrid solar cell which is prepared by adopting the method. As shown in FIG. 1, the silicon-based organic-inorganic hybrid solar cell comprises a back electrode 1, a lithium fluoride layer 2, an N-type monocrystalline silicon substrate 3, a silicon wire array 4, a Spiro-OMeTAD layer 5 (comprising a first Spiro-OMeTAD layer and a second Spiro-OMeTAD layer), a first PEDOT: PSS layer 6 and a front electrode 7 from bottom to top.
Example 1:
a preparation method of a silicon-based organic-inorganic hybrid solar cell comprises the following steps:
1) providing an N-type monocrystalline silicon substrate, preparing a silicon wire array on the upper surface of the N-type monocrystalline silicon substrate, wherein the length of a silicon wire in the silicon wire array is 4 micrometers, the diameter of the silicon wire is 800 nanometers, the distance between adjacent silicon nanowires is 1.5 micrometers, and in the step 1, preparing the silicon wire array on the upper surface of the N-type monocrystalline silicon substrate by wet etching by using a PS ball as a mask.
2) And then passivating the N-type monocrystalline silicon substrate, wherein the specific steps of passivating the N-type monocrystalline silicon substrate are as follows: soaking the N-type monocrystalline silicon substrate in HF for 6 minutes, then chlorinating the hydrogenated N-type monocrystalline silicon substrate to change a silicon-hydrogen bond into a silicon-chlorine bond, and then methylating the N-type monocrystalline silicon substrate to change the silicon-chlorine bond into a silicon-carbon bond to passivate the N-type monocrystalline silicon substrate.
3) Preparation of the first Spiro-OMeTAD layer: at a pressure of 1.0X 105In a closed cavity Pa, dripping a first Spiro-OMeTAD solution on the N-type monocrystalline silicon substrate obtained in the step 2, standing for 1.5 minutes, and keeping the pressure in the closed cavity from 1.0 multiplied by 10 in the standing process5Pa is gradually increased to 1.3X 105Pa, then at a pressure of 1.3X 105Spin coating is carried out for 80 seconds under the condition of Pa, and then first annealing treatment is carried out to form a first Spiro-OMeTAD layer.
In the step 3), the concentration of the Spiro-OMeTAD in the first Spiro-OMeTAD solution is 15mg/ml, the rotation speed of the first Spiro-OMeTAD solution in the spin coating process is 2500 rpm, and the first annealing process specifically comprises the following steps: at a pressure of 1.3X 105Heat treatment is carried out for 12 minutes under the condition of Pa and at the temperature of 85 ℃.
4) Preparation of a second spiral-OMeTAD layer: at a pressure of 1.3X 105In a closed cavity Pa, dripping a second Spiro-OMeTAD solution on the N-type monocrystalline silicon substrate obtained in the step 3, standing for 1 minute, and keeping the pressure in the closed cavity from 1.3 multiplied by 10 in the standing process5Pa is gradually increased to 1.6X 105Pa, then at a pressure of 1.6X 105Spin coating under Pa for 80 seconds, and then performingAnd carrying out second annealing treatment to form a second Spiro-OMeTAD layer.
In the step 4), the concentration of the Spiro-OMeTAD in the second Spiro-OMeTAD solution is 7mg/ml, the rotation speed of the second Spiro-OMeTAD solution in the spin coating process is 3500 rpm, and the second annealing process specifically comprises the following steps: at a pressure of 1.6X 105Heat treatment is carried out for 18 minutes under the condition of Pa and at the temperature of 90 ℃.
5) Preparation of the first PEDOT: PSS layer: at a pressure of 1.0X 105In a closed cavity of Pa, dripping the PEDOT/PSS solution on the N-type monocrystalline silicon substrate obtained in the step 4, standing for 1.5 minutes, and keeping the pressure in the closed cavity from 1.0 multiplied by 10 in the standing process5Pa is gradually increased to 1.5X 105Pa, then at a pressure of 1.5X 105Spin coating for 70 seconds under the Pa condition, and then carrying out third annealing treatment to form a first PEDOT PSS layer.
PSS solution is coated at 3000 r/min, and the third annealing treatment comprises the following specific steps: at a pressure of 1.5X 105Heat treatment is carried out for 25 minutes under the condition of Pa and under the condition of 130 ℃.
6) And (5) preparing a front electrode on the N-type monocrystalline silicon substrate obtained in the step (5), wherein the method for forming the front electrode is thermal evaporation, the front electrode is made of copper, the thickness of the front electrode is 120 nanometers, and the front electrode is a gate electrode.
7) And (6) evaporating a lithium fluoride layer on the back surface of the N-type monocrystalline silicon substrate obtained in the step (6), wherein the thickness of the lithium fluoride layer is 1.5 nanometers.
8) And (4) preparing a back electrode on the back side of the N-type monocrystalline silicon substrate obtained in the step (7), wherein the method for forming the back electrode is thermal evaporation, the material of the back electrode is aluminum, and the thickness of the back electrode is 150 nanometers.
The silicon-based organic-inorganic hybrid solar cell prepared by the method has the open-circuit voltage of 0.61V and the short-circuit current of 35.8mA/cm2The fill factor was 0.75, and the photoelectric conversion efficiency was 16.4%.
Example 2
A preparation method of a silicon-based organic-inorganic hybrid solar cell comprises the following steps:
1) providing an N-type monocrystalline silicon substrate, preparing a silicon wire array on the upper surface of the N-type monocrystalline silicon substrate, wherein the length of a silicon wire in the silicon wire array is 2 micrometers, the diameter of the silicon wire is 600 nanometers, the distance between adjacent silicon nanowires is 1 micrometer, and in the step 1, preparing the silicon wire array on the upper surface of the N-type monocrystalline silicon substrate through dry etching.
2) And then passivating the N-type monocrystalline silicon substrate, wherein the specific steps of passivating the N-type monocrystalline silicon substrate are as follows: soaking the N-type monocrystalline silicon substrate in HF for 6 minutes, then chlorinating the hydrogenated N-type monocrystalline silicon substrate to change a silicon-hydrogen bond into a silicon-chlorine bond, and then methylating the N-type monocrystalline silicon substrate to change the silicon-chlorine bond into a silicon-carbon bond to passivate the N-type monocrystalline silicon substrate.
3) Preparation of the first Spiro-OMeTAD layer: at a pressure of 1.0X 105In a closed cavity Pa, dripping a first Spiro-OMeTAD solution on the N-type monocrystalline silicon substrate obtained in the step 2, standing for 2 minutes, and keeping the pressure in the closed cavity from 1.0 multiplied by 10 in the standing process5Pa is gradually increased to 1.3X 105Pa, then at a pressure of 1.3X 105Spin coating is carried out for 90 seconds under the condition of Pa, and then first annealing treatment is carried out to form a first Spiro-OMeTAD layer.
In the step 3), the concentration of the Spiro-OMeTAD in the first Spiro-OMeTAD solution is 20mg/ml, the rotation speed of the first Spiro-OMeTAD solution in the spin coating process is 3000 r/min, and the first annealing process specifically comprises the following steps: at a pressure of 1.3X 105Heat treatment is carried out for 15 minutes under the condition of Pa and at the temperature of 90 ℃.
4) Preparation of a second spiral-OMeTAD layer: at a pressure of 1.3X 105In a closed cavity Pa, dripping a second Spiro-OMeTAD solution on the N-type monocrystalline silicon substrate obtained in the step 3, standing for 2 minutes, and keeping the pressure in the closed cavity from 1.3 multiplied by 10 in the standing process5Pa is gradually increased to 1.6X 105Pa, then at a pressure of 1.6X 105Spin coating under Pa for 90 seconds, thenAnd then carrying out second annealing treatment to form a second Spiro-OMeTAD layer.
In the step 4), the concentration of the Spiro-OMeTAD in the second Spiro-OMeTAD solution is 10mg/ml, the rotation speed of the second Spiro-OMeTAD solution in the spin coating process is 4000 revolutions per minute, and the second annealing process specifically comprises the following steps: at a pressure of 1.6X 105Heat treatment is carried out for 20 minutes under the condition of Pa and at the temperature of 95 ℃.
5) Preparation of the first PEDOT: PSS layer: at a pressure of 1.0X 105In a closed cavity of Pa, dripping the PEDOT/PSS solution on the N-type monocrystalline silicon substrate obtained in the step 4, standing for 2 minutes, and keeping the pressure in the closed cavity from 1.0 multiplied by 10 in the standing process5Pa is gradually increased to 1.5X 105Pa, then at a pressure of 1.5X 105Spin coating for 90 seconds under the Pa condition, and then carrying out third annealing treatment to form a first PEDOT PSS layer.
PSS solution is coated at 3500 rpm, and the third annealing treatment comprises the following specific steps: at a pressure of 1.5X 105Heat treatment is carried out for 30 minutes under the condition of Pa and under the condition of 140 ℃.
6) And (5) preparing a front electrode on the N-type monocrystalline silicon substrate obtained in the step (5), wherein the method for forming the front electrode is thermal evaporation, the front electrode is made of silver, the thickness of the front electrode is 90 nanometers, and the front electrode is a gate electrode.
7) And (6) evaporating a lithium fluoride layer on the back surface of the N-type monocrystalline silicon substrate obtained in the step (6), wherein the thickness of the lithium fluoride layer is 1 nanometer.
8) And (4) preparing a back electrode on the back side of the N-type monocrystalline silicon substrate obtained in the step (7), wherein the method for forming the back electrode is thermal evaporation, the material of the back electrode is aluminum, and the thickness of the back electrode is 200 nanometers.
The silicon-based organic-inorganic hybrid solar cell prepared by the method has the open-circuit voltage of 0.59V and the short-circuit current of 34.9mA/cm2The fill factor was 0.74, and the photoelectric conversion efficiency was 15.2%.
Comparative example:
in order to highlight that the silicon-based organic-inorganic hybrid solar cell of the invention has excellent photoelectric conversion efficiency, as a comparison, a preparation method of a conventional silicon-based organic-inorganic hybrid solar cell comprises the following steps: 1) providing an N-type monocrystalline silicon substrate, preparing a silicon wire array on the upper surface of the N-type monocrystalline silicon substrate, wherein the length of a silicon wire in the silicon wire array is 4 micrometers, the diameter of the silicon wire is 800 nanometers, the distance between adjacent silicon nanowires is 1.5 micrometers, and in the step 1, preparing the silicon wire array on the upper surface of the N-type monocrystalline silicon substrate by wet etching by using a PS ball as a mask. 2) And then passivating the N-type monocrystalline silicon substrate, wherein the specific steps of passivating the N-type monocrystalline silicon substrate are as follows: soaking the N-type monocrystalline silicon substrate in HF for 6 minutes, then chlorinating the hydrogenated N-type monocrystalline silicon substrate to change a silicon-hydrogen bond into a silicon-chlorine bond, and then methylating the N-type monocrystalline silicon substrate to change the silicon-chlorine bond into a silicon-carbon bond to passivate the N-type monocrystalline silicon substrate. 3) Preparation of a Spiro-OMeTAD layer: spin-coating a Spiro-OMeTAD solution with a concentration of 20mg/ml for 80 seconds at a rotation speed of 2500 rpm, and then heat-treating at 85 ℃ for 20 minutes to form a Spiro-OMeTAD layer. 4) Preparation of PEDOT: PSS layer: and (3) spin-coating the PEDOT PSS solution for 70 seconds at the rotating speed of 3000 r/min, and carrying out heat treatment at the temperature of 130 ℃ for 25 minutes to form the PEDOT PSS layer. 5) And (4) preparing a front electrode on the N-type monocrystalline silicon substrate obtained in the step (4), wherein the method for forming the front electrode is thermal evaporation, the front electrode is made of copper, the thickness of the front electrode is 120 nanometers, and the front electrode is a gate electrode. 6) And (5) preparing a back electrode on the back of the N-type monocrystalline silicon substrate obtained in the step (5), wherein the method for forming the back electrode is thermal evaporation, the material of the back electrode is aluminum, and the thickness of the back electrode is 150 nanometers.
The silicon-based organic-inorganic hybrid solar cell prepared by the method has the open-circuit voltage of 0.6V and the short-circuit current of 31.8mA/cm2The fill factor was 0.71, and the photoelectric conversion efficiency was 13.5%.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (9)
1. A preparation method of a silicon-based organic-inorganic hybrid solar cell is characterized by comprising the following steps: the method comprises the following steps:
1) providing an N-type monocrystalline silicon substrate, and preparing a silicon wire array on the upper surface of the N-type monocrystalline silicon substrate, wherein the length of a silicon wire in the silicon wire array is 2-5 microns, the diameter of the silicon wire is 600-900 nanometers, and the distance between adjacent silicon nanowires is 1-2 microns;
2) then passivating the N-type monocrystalline silicon substrate;
3) preparation of the first Spiro-OMeTAD layer: at a pressure of 1.0X 105In a closed cavity Pa, dripping a first Spiro-OMeTAD solution on the N-type monocrystalline silicon substrate obtained in the step 2, standing for 1-2 minutes, and keeping the pressure in the closed cavity from 1.0 multiplied by 10 in the standing process5Pa is gradually increased to 1.3X 105Pa, then at a pressure of 1.3X 105Spin-coating for 60-90 seconds under the Pa condition, and then carrying out first annealing treatment to form a first Spiro-OMeTAD layer;
4) preparation of a second spiral-OMeTAD layer: at a pressure of 1.3X 105In a closed cavity Pa, dripping a second Spiro-OMeTAD solution on the N-type monocrystalline silicon substrate obtained in the step 3, standing for 1-2 minutes, and keeping the pressure in the closed cavity from 1.3 multiplied by 10 in the standing process5Pa is gradually increased to 1.6X 105Pa, then at a pressure of 1.6X 105Spin-coating for 60-90 seconds under the Pa condition, and then carrying out second annealing treatment to form a second Spiro-OMeTAD layer;
5) preparation of the first PEDOT: PSS layer: at a pressure of 1.0X 105In a closed cavity of Pa, dripping the PEDOT/PSS solution on the N-type monocrystalline silicon substrate obtained in the step 4, standing for 1-2 minutes, and keeping the pressure in the closed cavity from 1.0 multiplied by 10 in the standing process5Pa is gradually increased to 1.5X 105Pa, then at a pressure of 1.5X 105Spin coating under Pa60-90 seconds, and then carrying out third annealing treatment to form a first PEDOT PSS layer;
6) preparing a front electrode on the N-type monocrystalline silicon substrate obtained in the step 5;
7) evaporating a lithium fluoride layer on the back surface of the N-type monocrystalline silicon substrate obtained in the step 6;
8) and (4) preparing a back electrode on the back of the N-type monocrystalline silicon substrate obtained in the step (7).
2. The method for preparing silicon-based organic-inorganic hybrid solar cell according to claim 1, wherein: in the step 1, the silicon wire array is prepared on the upper surface of the N-type monocrystalline silicon substrate through wet etching or dry etching.
3. The method for preparing silicon-based organic-inorganic hybrid solar cell according to claim 1, wherein: in the step 2), the specific step of passivating the N-type monocrystalline silicon substrate is as follows: soaking the N-type monocrystalline silicon substrate in HF for 3-10 minutes, then chlorinating the hydrogenated N-type monocrystalline silicon substrate to change a silicon-hydrogen bond into a silicon-chlorine bond, and then methylating the N-type monocrystalline silicon substrate to change the silicon-chlorine bond into a silicon-carbon bond to passivate the N-type monocrystalline silicon substrate.
4. The method for preparing silicon-based organic-inorganic hybrid solar cell according to claim 1, wherein: in the step 3), the concentration of the Spiro-OMeTAD in the first Spiro-OMeTAD solution is 10-20mg/ml, the rotation speed of the first Spiro-OMeTAD solution in the spin coating process is 2000-3000 r/min, and the specific steps of the first annealing process are as follows: at a pressure of 1.3X 105Heat treatment is carried out for 10-15 minutes under the condition of Pa and the temperature of 80-90 ℃.
5. The method for preparing silicon-based organic-inorganic hybrid solar cell according to claim 1, wherein: in the step 4), the concentration of the Spiro-OMeTAD in the second Spiro-OMeTAD solution is 5-10mg/ml, and spin coating is carried outThe rotation speed of the second cyclone-OMeTAD solution is 3000-: at a pressure of 1.6X 105Heat treatment is carried out for 15-20 minutes under the condition of Pa and the temperature of 85-95 ℃.
6. The method for preparing silicon-based organic-inorganic hybrid solar cell according to claim 1, wherein: in the step 5), the rotation speed of the PEDOT/PSS solution is 2500-: at a pressure of 1.5X 105Heat treatment is carried out for 20-30 minutes under the condition of Pa and the temperature of 120-140 ℃.
7. The method for preparing silicon-based organic-inorganic hybrid solar cell according to claim 1, wherein: in the step 6), a method for forming the front electrode is one of thermal evaporation, magnetron sputtering and electron beam evaporation, the material of the front electrode is copper or silver, the thickness of the front electrode is 90-150 nm, and the front electrode is a gate electrode.
8. The method for preparing silicon-based organic-inorganic hybrid solar cell according to claim 1, wherein: in the step 7), the thickness of the lithium fluoride layer is 1-2 nm, in the step 8), the method for forming the back electrode is one of thermal evaporation, magnetron sputtering and electron beam evaporation, the material of the back electrode is aluminum, and the thickness of the back electrode is 100-200 nm.
9. A silicon-based organic-inorganic hybrid solar cell, characterized in that the silicon-based organic-inorganic hybrid solar cell is prepared by the method of any one of claims 1 to 8.
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