CN109801991B - Vertical laminated solar cell and preparation method thereof - Google Patents
Vertical laminated solar cell and preparation method thereof Download PDFInfo
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- CN109801991B CN109801991B CN201910006482.4A CN201910006482A CN109801991B CN 109801991 B CN109801991 B CN 109801991B CN 201910006482 A CN201910006482 A CN 201910006482A CN 109801991 B CN109801991 B CN 109801991B
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Abstract
The invention discloses a vertical laminated solar cell and a preparation method thereof, wherein the cell sequentially comprises the following components from top to bottom: the width of the bottom layer cell is smaller than that of the middle layer cell. The invention utilizes the novel two-dimensional semiconductor material to prepare the top layer battery and the bottom layer battery, can realize the absorption of sunlight by using smaller thickness, reduces the material usage amount, reduces the manufacturing cost, can reduce the electrical loss of the solar battery, and improves the conversion efficiency of the solar battery. In addition, the vertical multi-junction structure is adopted, namely a plurality of pn junctions are connected in series, so that the output voltage is high, the output current can be reduced by reducing the area of the periodically repeated basic unit of the battery, and the grid-connected power generation is more suitable.
Description
Technical Field
The present disclosure relates to solar cell structures and methods for fabricating the same, and more particularly, to a vertical tandem solar cell and a method for fabricating the same.
Background
In recent years, the problems of environmental pollution, greenhouse effect and the like around the world become more and more serious, the traditional energy reserves are less and less, the price is higher and higher, so the requirement of human beings on clean energy is greater and greater, and the solar photovoltaic power generation is more and more emphasized by people as the clean energy. At present, most of solar photovoltaic cells sold in the market are crystalline silicon solar cells, and the power generation cost of the solar photovoltaic cells is still higher than that of traditional fossil energy. The power generation cost of the crystalline silicon battery can be reduced by improving the conversion efficiency of the crystalline silicon battery, but the efficiency of the crystalline silicon battery is close to the theoretical limit at present, and the space for improving the efficiency is very limited. The reason is that the long and short wavelength portions of the solar spectrum are not efficiently utilized by crystalline silicon materials, and attempts have been made to fabricate the top cell on the top surface of crystalline silicon using other semiconductor materials having a larger band width than crystalline silicon and the bottom cell on the bottom surface of crystalline silicon using other semiconductor materials having a smaller band width than crystalline silicon. The top layer cell, the bottom layer cell and the crystalline silicon cell of the middle layer form a laminated solar cell, so that the conversion efficiency of the crystalline silicon solar cell is improved. People mainly adopt III-V semiconductor materials to prepare a top battery and utilize germanium materials to prepare a bottom battery at present, and the cost of the two materials is higher. The sub-cells of the traditional laminated solar cell are electrically connected in a current matching mode, and current mismatch is easily generated among the sub-cells along with the change of the incident angle and the spectrum of incident sunlight, so that power loss is caused. In addition, the single-chip output voltage of the crystalline silicon solar cell sold in the market at present is low (less than 0.8V), and the crystalline silicon solar cell can be used for grid-connected power generation only by being connected in series.
Disclosure of Invention
The invention aims to provide a vertical laminated solar cell and a preparation method of the vertical laminated solar cell.
The technical scheme of the invention is as follows:
a vertical laminate solar cell, the cell comprising in order from top to bottom: the width of the bottom layer cell is smaller than that of the middle layer cell.
Further, the top layer battery comprises: the substrate comprises a periodically repeated basic unit, two side doped regions, two side electrodes and an antireflection layer, wherein the periodically repeated basic unit comprises:
the first base region is a single-layer or multi-layer tungsten disulfide material, and the thickness of the first base region is from 1 layer to 100 layers;
the first doping region is made of a single-layer or multi-layer tungsten disulfide material, is formed on one side of the first base region, and has the same thickness as that of the first base region;
the second doping region is made of a single-layer or multi-layer tungsten disulfide material, is formed on the other side of the first base region, and has the same thickness as that of the first base region;
two adjacent basic units are connected in series through a first doping area and a second doping area;
the two doped regions are:
the third doping area is made on the outer side of the first doping area of the basic unit on the outermost side, and the thickness of the third doping area is the same as that of the first doping area;
the fourth doping area is made of a single-layer or multi-layer tungsten disulfide material, is arranged on the outer side of the second doping area of the basic unit on the other outermost side, and has the same thickness as that of the second doping area;
the electrodes on both sides are:
the first electrode is manufactured on the upper surface of the third doped region, and the width of the first electrode is smaller than that of the third doped region;
the second electrode is manufactured on the upper surface of the fourth doped region, and the width of the second electrode is smaller than that of the fourth doped region;
and the antireflection layer is manufactured on the upper surface of the periodically repeated basic unit, covers the end parts of the third doped region and the fourth doped region and is connected with the first electrode and the second electrode.
Further, the interlayer cell includes: the device comprises a periodically repeated basic unit, two-side doped regions, two-side electrodes, a first isolation layer and a second isolation layer, wherein the periodically repeated basic unit comprises:
the second base region is made of monocrystalline silicon material and is less than 400 microns thick;
the fifth doped region is made of a single crystal silicon material, is formed on one side of the second base region and has the same thickness as that of the second base region;
the sixth doped region is made of a single crystal silicon material, is made on the other side of the second base region, and has the same thickness as that of the second base region;
two adjacent basic units are connected in series through a fifth doping area and a sixth doping area;
the two doped regions are:
the seventh doped region is made of single crystal silicon material, is manufactured at the outer side of the fifth doped region of the basic unit at the outermost side, and has the same thickness as that of the fifth doped region;
the eighth doped region is made of single crystal silicon material, is manufactured at the outer side of the sixth doped region of the basic unit at the other outermost side and has the same thickness as that of the sixth doped region;
the electrodes on both sides are:
the third electrode is manufactured on the lower surface of the seventh doped region, and the width of the third electrode is smaller than that of the seventh doped region;
the fourth electrode is manufactured on the lower surface of the eighth doped region, and the width of the fourth electrode is smaller than that of the eighth doped region;
the first isolation layer is manufactured on the upper surface of the periodically repeated basic unit, covers the seventh doping area and the eighth doping area, is positioned on the lower surface of the periodically repeated basic unit of the top battery, and covers the third doping area and the fourth doping area of the top battery;
and the second isolation layer is manufactured on the lower surface of the periodically repeated basic unit, covers the end parts of the seventh doped region and the eighth doped region, and is connected with the third electrode and the fourth electrode.
Further, the bottom layer battery includes: the periodic repeated basic unit, the two-side doped region, the two-side electrode, the third isolation layer and the back reflection layer are arranged on the same plane, wherein the periodic repeated basic unit and the two-side doped region are arranged in the middle position of the lower surface of the second isolation layer of the middle-layer cell, the width of the periodic repeated basic unit is smaller than that of the second isolation layer, and the periodic repeated basic unit comprises:
the third base region is a plurality of layers of black phosphorus materials, and the thickness of the third base region is from 2 layers to 1000 layers;
the ninth doped region is made of a multi-layer black phosphorus material, is formed on one side of the third base region, and has the same thickness as that of the third base region;
the tenth doping area is made of a plurality of layers of black phosphorus materials, is formed on the other side of the third base area, and has the same thickness as that of the third base area;
two adjacent basic units are connected in series through a ninth doped region and a tenth doped region;
the two doped regions are:
the eleventh doping area is made of a multi-layer black phosphorus material, is arranged on the outer side of the ninth doping area of the basic unit on the outermost side, and has the same thickness as that of the ninth doping area;
the twelfth doped region is made of a plurality of layers of black phosphorus materials, is arranged at the outer side of the tenth doped region of the basic unit at the other outermost side, and has the same thickness as that of the tenth doped region;
the electrodes on both sides are:
the fifth electrode is manufactured on the lower surface of the eleventh doping region, and the width of the fifth electrode is smaller than that of the eleventh doping region;
the sixth electrode is manufactured on the lower surface of the twelfth doped region, and the width of the sixth electrode is smaller than that of the twelfth doped region;
the third isolation layer is manufactured on the lower surface of the periodically repeated basic unit, covers the end parts of the eleventh doped region and the twelfth doped region, and is connected with the fifth electrode and the sixth electrode;
and the back reflecting layer is manufactured on the lower surface of the third isolating layer, covers the third isolating layer and is connected with the fifth electrode and the sixth electrode.
A method of fabricating a vertical tandem solar cell, the method comprising the steps of:
step 1: preparing a second base region, a fifth doping region, a sixth doping region, a seventh doping region and an eighth doping region on two sides, a first isolation layer and a second isolation layer of a periodically repeated basic unit of the middle-layer cell;
step 2: preparing a first base region, a first doping region, a second doping region, a third doping region and a fourth doping region on two sides and an antireflection film of a periodically repeated basic unit of the top layer cell on the upper surface of the middle layer cell;
and step 3: preparing a third base region, a ninth doped region, a tenth doped region, eleventh doped regions and twelfth doped regions on two sides, a third isolation layer and a back reflection layer of a periodically repeated basic unit of the bottom layer cell at the middle position of the lower surface of the middle layer cell;
and 4, step 4: preparing a first electrode on the upper surface of the third doped region, preparing a second electrode on the upper surface of the fourth doped region, preparing a third electrode on the lower surface of the seventh doped region, preparing a fourth electrode on the lower surface of the eighth doped region, preparing a fifth electrode on the lower surface of the eleventh doped region, and preparing a sixth electrode on the lower surface of the twelfth doped region.
The invention has the beneficial effects that:
1. utilize novel two-dimensional semiconductor material individual layer and multilayer tungsten disulfide to replace traditional three five semiconductor materials to prepare top layer battery, the optical absorption coefficient of individual layer and multilayer tungsten disulfide is greater than three five semiconductor materials, can utilize less thickness to realize the absorption to the sunlight to can reduce the material use amount, reduce manufacturing cost, and can reduce solar cell's electricity loss, improve solar cell's conversion efficiency.
2. Utilize novel two-dimensional semiconductor material multilayer black phosphorus to replace traditional germanium material preparation bottom battery, the optical absorption coefficient of multilayer black phosphorus is greater than the germanium material, can utilize less thickness to realize the absorption to the sunlight to can reduce the material use amount, reduce manufacturing cost, and can reduce solar cell's electricity loss, improve solar cell's conversion efficiency.
3. The invention relates to a vertical laminated solar cell, comprising three components: the top layer cell, the middle layer cell and the bottom layer cell all adopt a vertical multi-junction structure, namely a plurality of pn junctions are connected in series, so the output voltage is high, the output current can be reduced by reducing the area of a periodically repeated basic unit of the cell, and therefore the cell is more suitable for grid-connected power generation than the current crystalline silicon solar cell.
4. The top layer cell, the middle layer cell and the bottom layer cell can work independently and generate power independently, and the positive electrodes and the negative electrodes of the three sub-cells can be connected, namely, the negative electrodes and the negative electrodes are electrically connected in a voltage matching mode. Along with the change of the incident angle and the spectrum of the incident sunlight, the voltage mismatch generated among the sub-cells is smaller and far smaller than the current mismatch, and the generated electrical loss is far smaller than the current matching condition.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present patent more apparent, the following detailed description is given in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic diagram of a vertical tandem solar cell;
FIG. 2 is a flow chart of the preparation of the present invention.
Detailed Description
Referring to fig. 1 and 2, the present invention provides a vertical stacked solar cell, which comprises, in order from top to bottom: the width of the bottom layer cell is smaller than that of the middle layer cell.
Wherein the top layer cell comprises: the substrate comprises a periodically repeated basic unit, two side doped regions, two side electrodes and an antireflection layer, wherein the periodically repeated basic unit comprises:
the first base region 10 is a single-layer tungsten disulfide material;
the first doping region 11 is a single-layer tungsten disulfide material, the first doping region 11 is manufactured on one side of the first base region 10 and is doped in an N type, and chlorine atoms are doped in the first doping region;
the second doped region 12 is a single-layer tungsten disulfide material, the second doped region 12 is made on the other side of the first base region 10 and is doped in a P-type manner, and niobium atoms are doped in the second doped region;
two adjacent basic units are connected in series through a first doping area 11 and a second doping area 12;
the two doped regions are:
the third doped region 13 is a single-layer tungsten disulfide material, the third doped region 13 is manufactured at the outer side of the first doped region 11 of the basic unit at the outermost side, is doped in an N type, is doped with chlorine atoms, and the doping concentration of the third doped region 13 is greater than that of the first doped region 11;
a fourth doped region 14, which is a single layer of tungsten disulfide material, the fourth doped region 14 is manufactured at the outer side of the second doped region 12 of the other outermost basic unit, and is doped P-type, the doping concentration of the fourth doped region 14 is greater than that of the second doped region 12, and the doping is niobium atoms;
the electrodes on both sides are:
a first electrode 15, wherein the first electrode 15 is formed on the upper surface of the third doped region 13, the width of the first electrode 15 is smaller than that of the third doped region 13, the first electrode 15 is made of a laminated layer of titanium and gold, the thickness of titanium is 30 nanometers, and the thickness of gold is 50 nanometers;
a second electrode 16, wherein the second electrode 16 is formed on the upper surface of the fourth doped region 14, the width of the second electrode 16 is smaller than the width of the fourth doped region 14, the second electrode 16 is made of a laminated layer of titanium and gold, the thickness of titanium is 30 nanometers, and the thickness of gold is 50 nanometers;
an anti-reflection layer 17, wherein the anti-reflection layer 17 is made on the upper surface of the periodically repeated basic units, covers the end parts of the third doped region 13 and the fourth doped region 14, is connected with the first electrode 15 and the second electrode 16, and the material of the anti-reflection layer 17 is SiO2The thickness is 100 nm.
In the vertical tandem solar cell of the present invention, the intermediate layer cell includes: the device comprises a periodically repeated basic unit, two-side doped regions, two-side electrodes, a first isolation layer and a second isolation layer, wherein the periodically repeated basic unit comprises:
the second base region 20 is made of monocrystalline silicon material and has a thickness of 200 microns;
a fifth doped region 21 made of a single crystal silicon material and having a thickness of 200 μm, the fifth doped region 21 being formed on one side of the second base region 20 and doped with N-type dopants and phosphorus atoms;
a sixth doped region 22 made of a single crystal silicon material and having a thickness of 200 μm, the sixth doped region 22 being formed on the other side of the second base region 20 and doped with P-type dopants, and boron atoms;
two adjacent basic units are connected in series through a fifth doping area 21 and a sixth doping area 22;
the two doped regions are:
a seventh doped region 23 made of a single crystal silicon material and having a thickness of 200 μm, the seventh doped region 23 being formed outside the fifth doped region 21 of the outermost basic unit and doped with N-type dopant, wherein the dopant concentration of the seventh doped region 23 is greater than the dopant concentration of the fifth doped region 21;
an eighth doped region 24 made of a single crystal silicon material and having a thickness of 200 μm, the eighth doped region 24 being formed outside the sixth doped region 22 of the other outermost basic unit and doped with P-type doping, boron atoms being doped, and a doping concentration of the eighth doped region 24 being greater than a doping concentration of the sixth doped region 22;
the electrodes on both sides are:
a third electrode 25, wherein the third electrode 25 is formed on the lower surface of the seventh doped region 23, the width of the third electrode 25 is smaller than that of the seventh doped region 23, the third electrode 25 is made of a laminated layer of titanium and gold, the thickness of the titanium is 30 nanometers, and the thickness of the gold is 50 nanometers;
a fourth electrode 26, wherein the fourth electrode 26 is formed on the lower surface of the eighth doped region 24, the width of the fourth electrode 26 is smaller than that of the eighth doped region 24, the fourth electrode 26 is made of a laminated layer of titanium and gold, the thickness of titanium is 30 nanometers, and the thickness of gold is 50 nanometers;
a first isolation layer 27, wherein the first isolation layer 27 is formed on the upper surface of the periodically repeating basic unit, covers the seventh doping region 23 and the eighth doping region 24, the first isolation layer 27 is located on the lower surface of the periodically repeating basic unit of the top cell, covers the third doping region 13 and the fourth doping region 14 of the top cell, and the material of the first isolation layer 27 is SiO2A thickness of 50 nm;
a second isolation layer 28, wherein the second isolation layer 28 is formed on the lower surface of the periodically repeated basic unit, covers the end portions of the seventh doped region 23 and the eighth doped region 24, and is connected with the third electrode 25 and the fourth electrode 26, and the material of the second isolation layer 28 is SiO2The thickness was 50 nm.
In the vertical stacked solar cell of the present invention, the bottom layer cell includes: the periodic repeating basic unit, the two-side doped region, the two-side electrode, the third isolation layer and the back reflection layer are five parts, wherein the periodic repeating basic unit and the two-side doped region are located in the middle position of the lower surface of the second isolation layer 28 of the middle layer cell, the width of the periodic repeating basic unit and the two-side doped region is smaller than that of the second isolation layer 28, and the periodic repeating basic unit comprises:
the third base region 30 is 3 layers of black phosphorus materials;
a ninth doped region 31 made of 3 layers of black phosphorus material, wherein the ninth doped region 31 is formed on one side of the third base region 30 and is doped with N-type doping, and aluminum atoms are doped;
a tenth doped region 32 made of 3 layers of black phosphorus materials, wherein the tenth doped region 32 is formed on the other side of the third base region 30 and is doped with P-type selenium atoms;
two adjacent basic units are connected in series through a ninth doped region 31 and a tenth doped region 32;
the two doped regions are:
an eleventh doped region 33, which is 3 layers of black phosphorus material, wherein the eleventh doped region 33 is formed outside the ninth doped region 31 of the outermost basic unit, and is doped with N-type doping, aluminum atoms are doped, and the doping concentration of the eleventh doped region 33 is greater than that of the ninth doped region 31;
a twelfth doped region 34, which is 3 layers of black phosphorus material, the twelfth doped region 34 is manufactured at the outer side of the tenth doped region 32 of the other outermost basic unit, and is doped P-type, selenium atoms are doped, and the doping concentration of the twelfth doped region 34 is greater than that of the tenth doped region 32;
the electrodes on both sides are:
a fifth electrode 35, wherein the fifth electrode 35 is formed on the lower surface of the eleventh doped region 33, the width of the fifth electrode 35 is smaller than that of the eleventh doped region 33, the fifth electrode 35 is made of a laminated layer of titanium and gold, the thickness of titanium is 30 nanometers, and the thickness of gold is 50 nanometers;
a sixth electrode 36, the sixth electrode 36 being formed on the lower surface of the twelfth doped region 34, the sixth electrode 36 having a width smaller than the width of the twelfth doped region 34, the sixth electrode 36 being made of a laminate of titanium and gold, the thickness of the titanium being 30 nm, and the thickness of the gold being 50 nm;
a third isolation layer 37, wherein the third isolation layer 37 is formed on the lower surface of the periodically repeated basic unit, covers the periodically repeated basic unit, and covers the eleventh doped region 33 and the twelfth doped regionThe end of the impurity region 34 is connected to the fifth electrode 35 and the sixth electrode 36, and the material of the third isolation layer 37 is SiO2A thickness of 50 nm;
a back reflection layer 38, the back reflection layer 38 is formed on the lower surface of the third isolation layer 37, covers the third isolation layer 37, and is connected to the fifth electrode 35 and the sixth electrode 36, the back reflection layer 38 is made of aluminum, and the thickness of the back reflection layer 38 is 200 nm.
The cell, in use, connects together the first electrode 15, the third electrode 25 and the fifth electrode 35 as a negative electrode; the second electrode 16, the fourth electrode 26 and the sixth electrode 36 are connected together to serve as a positive electrode, and the output voltages of the three sub-cells are close to each other by adjusting the number and the width of the periodically repeated units of the top layer cell, the middle layer cell and the bottom layer cell.
The invention provides a preparation method of a vertical laminated solar cell, which comprises the following steps:
step 1: a second base region 20, a fifth doped region 21, a sixth doped region 22, seventh and eighth doped regions 23, 24 on both sides, a first isolation layer 27 and a second isolation layer 28 of the periodically repeated basic unit of the intermediate layer cell are prepared.
The step 1 comprises the following steps:
step 1-1: doping phosphorus atoms in the area near the surface of one surface of the monocrystalline silicon substrate by a thermal diffusion method, wherein the diffusion temperature is 850 ℃, and the diffusion source is phosphorus oxychloride to form a fifth doping area 21; and doping boron atoms in the area near the surface of the other surface of the monocrystalline silicon substrate by a diffusion method, wherein the diffusion temperature is 900 ℃, the diffusion source is boron tribromide to form a sixth doping area 22, and the undoped middle area of the monocrystalline silicon substrate is a second base area 20, so that the preparation of the basic substrate is completed.
Step 1-2: on the surface of the fifth doping area 21 of a basic substrate, a seventh doping area 23 is prepared by utilizing an atmospheric pressure epitaxy process, gases are introduced into the seventh doping area, namely trichlorosilane, phosphane and hydrogen, and the epitaxy temperature is 1150 ℃, so that the preparation of the first outer side substrate is completed.
Step 1-3: and preparing an eighth doped region 24 on the surface of the sixth doped region 22 of the other basic substrate by using an atmospheric pressure epitaxy process, introducing gases including trichlorosilane, borane and hydrogen, and finishing the preparation of the second outer substrate at an epitaxy temperature of 1150 ℃.
Step 1-4: a plurality of base substrates are sequentially stacked in the order that the fifth doped region 21 of one base substrate is adjacent to the sixth doped region 22 of another base substrate, the first outer substrate is placed on the uppermost portion of the stacked base substrates, and the second outer substrate is placed on the lowermost portion of the stacked base substrates, with the fifth doped regions 21 of all the substrates above and the sixth doped regions 22 below.
Step 1-5: putting the stacked substrates into a bonding machine, heating and pressing the substrates at 300 ℃ under 10MPa to bond the adjacent substrates together to form a whole.
Step 1-6: and sequentially cutting the bonds and the substrate which are integrated together by using a diamond sand wire along the direction vertical to the surface of the substrate to prepare a series of flaky rectangular vertical structures consisting of a plurality of periodically repeated basic units and two side doped regions.
Step 1-7: and etching off the damage layer on the surface of the vertical structure by using a mixed solution of nitric acid and hydrofluoric acid.
Step 1-8: the first isolation layer 27 and the second isolation layer 28 are prepared on two surfaces of the vertical structure by a thermal oxidation method, the oxidation temperature is 1050 ℃, and the oxidation gas is oxygen.
Step 2: preparing a first base region 10, a first doping region 11, a second doping region 12, third doping regions 13 and fourth doping regions 14 on two sides and an antireflection film 17 of a periodically repeated basic unit of the top layer cell on the upper surface of the middle layer cell.
The step 2 comprises the following steps:
step 2-1: preparing a single layer of tungsten disulfide on the upper surface of the first isolation layer 27 by chemical vapor deposition, wherein the source material is WO3Powder and S powder, gas is selected from H2And N2The gas flow rate was 20sccm and 60sccm, the deposition pressure was 2Pa, and the deposition temperature was 900 ℃.
Step 2-2: performing local reactive ion etching on the surface of the single-layer molybdenum disulfide by adopting a reactive ion etching process, wherein CH is selected as etching gas2Cl2Etching power of 50W, etching pressure of 1Pa, gas flow rate of 20sccm, etching time of 30 seconds, and doping Cl atoms locally to prepare the N-type first doping region 11 of the periodically repeated basic unit.
Performing local reactive ion etching on the surface of the single-layer molybdenum disulfide by adopting a reactive ion etching process, wherein CH is selected as etching gas2Cl2Etching power of 100W, etching pressure of 1Pa, gas flow rate of 20sccm, etching time of 60 seconds, and doping Cl atoms locally to prepare an N-type third doping region 13 outside the first doping region 11 of the basic unit at the outermost side.
Locally doping the monolayer tungsten disulfide by adopting an ion implantation process, wherein implanted atoms are niobium atoms, and the implantation dosage is 1 × 1015/cm2The implantation energy is 20keV, and then the rapid annealing is carried out for 10s under the nitrogen atmosphere, the annealing temperature is 500 ℃, and the P-type second doping area 12 of the basic unit which is periodically repeated is prepared.
Locally doping the monolayer tungsten disulfide by adopting an ion implantation process, wherein implanted atoms are niobium atoms, and the implantation dosage is 5 × 1015/cm2The implantation energy is 20keV, and then rapid annealing is performed for 10s at 500 degrees in a nitrogen atmosphere to prepare a P-type fourth doping region 14 outside the second doping region 12 of the other outermost basic cell.
And step 3: and preparing a third base region 30, a ninth doped region 31, a tenth doped region 32, eleventh doped regions 33 and twelfth doped regions 34 on two sides, a third isolation layer 37 and a back reflection layer 38 of the periodically repeated basic unit of the bottom layer cell in the middle of the lower surface of the middle layer cell.
The step 3 comprises the following steps:
step 3-1: preparing 3 layers of red phosphorus on the lower surface of the second isolation layer 28 by adopting a thermal evaporation method, wherein the evaporation source material is block black phosphorus, and the substrate heating temperature is 600 ℃; then putting the sample into a chemical vapor deposition device, wherein the source material is SnI4Powder and Sn powder, argon is selected as gas, the flow rate of the gas is 50sccm, the gas pressure is 2Pa,the deposition temperature is 900 ℃, and 3 layers of red phosphorus are changed into 3 layers of black phosphorus.
Step 3-2: and (3) locally doping aluminum atoms on the 3 layers of black phosphorus by adopting a thermal diffusion method, wherein a diffusion source is trimethyl aluminum, the diffusion temperature is 150 ℃, and an N-type ninth doping area 31 of a periodically repeated basic unit is prepared.
And (3) locally doping aluminum atoms on the 3 layers of black phosphorus by adopting a thermal diffusion method, wherein a diffusion source is trimethylaluminum, the diffusion temperature is 200 ℃, and an N-type eleventh doping region 33 outside the ninth doping region 31 of the outermost basic unit is prepared.
Locally doping selenium atoms on the 3 layers of black phosphorus by adopting an ion implantation method, wherein the implantation dosage is 1 × 1014/cm2The implantation energy is 20keV, and then rapid annealing is performed for 10s at 500 degrees under a nitrogen atmosphere to prepare a P-type tenth doping region 32 of a basic unit which is periodically repeated.
Locally doping selenium atoms on the 3-layer black phosphorus by adopting an ion implantation method, wherein the implantation dosage is 5 × 1014/cm2The implantation energy is 20keV, and then rapid annealing is performed for 10s at 500 degrees in a nitrogen atmosphere to prepare a P-type twelfth doping region 34 outside the tenth doping region 32 of the other outermost basic cell.
Step 3-3: deposition of SiO on periodically repeating elementary cell surfaces by means of chemical vapor deposition2Depositing film at 900 deg.c with SiH as depositing gas4，O2And H2The gas flow rate was 10sccm, and the deposition pressure was 1Pa to prepare the third spacer layer 37.
Step 3-4: and depositing an aluminum film on the surface of the third isolating layer 37 by using a magnetron sputtering process, wherein a sputtering target material is aluminum, the discharge power is 200W, a sputtering gas is argon, and the discharge pressure is 1Pa, so that the back reflecting layer 38 is prepared.
And 4, step 4: depositing a titanium film and a gold film on the upper surface of the third doped region 13, the upper surface of the fourth doped region 14, the lower surface of the seventh doped region 23, the lower surface of the eighth doped region 24, the lower surface of the eleventh doped region 33 and the lower surface of the twelfth doped region 36 by using a magnetron sputtering method, wherein a sputtering target material is selected from titanium and gold, the discharge power is 300W, the sputtering gas is selected from argon, and the discharge pressure is 1Pa, and preparing the first electrode 15, the second electrode 16, the third electrode 25, the fourth electrode 26, the fifth electrode 35 and the sixth electrode 36.
Claims (16)
1. A vertical laminate solar cell, comprising in order from top to bottom: the width of the bottom layer cell is smaller than that of the middle layer cell;
wherein the top layer cell comprises: the substrate comprises a periodically repeated basic unit, two side doped regions, two side electrodes and an antireflection layer, wherein the periodically repeated basic unit comprises:
the first base region (10) is a single-layer or multi-layer tungsten disulfide material, and the thickness of the first base region is from 1 layer to 100 layers;
the first doping region (11) is made of a single-layer or multi-layer tungsten disulfide material, the first doping region (11) is manufactured on one side of the first base region (10), and the thickness of the first doping region is the same as that of the first base region (10);
the second doping region (12) is made of a single-layer or multi-layer tungsten disulfide material, the second doping region (12) is manufactured on the other side of the first base region (10), and the thickness of the second doping region is the same as that of the first base region (10);
two adjacent basic units are connected in series through a first doping area (11) and a second doping area (12);
the two doped regions are:
the third doping area (13) is a single-layer or multi-layer tungsten disulfide material, and the third doping area (13) is manufactured on the outer side of the first doping area (11) of the basic unit at the outermost side and has the same thickness as that of the first doping area (11);
the fourth doping area (14) is a single layer or multiple layers of tungsten disulfide materials, the fourth doping area (14) is manufactured on the outer side of the second doping area (12) of the other outermost basic unit, and the thickness of the fourth doping area (14) is the same as that of the second doping area (12);
the electrodes on both sides are:
a first electrode (15), wherein the first electrode (15) is manufactured on the upper surface of the third doping area (13), and the width of the first electrode (15) is smaller than that of the third doping area (13);
the second electrode (16), the second electrode (16) is made on the upper surface of the fourth doped region (14), its width is smaller than the width of the fourth doped region (14);
and the antireflection layer (17) is manufactured on the upper surface of the periodically repeated basic unit, covers the end parts of the third doped region (13) and the fourth doped region (14), and is connected with the first electrode (15) and the second electrode (16).
2. The vertical tandem solar cell of claim 1, wherein: wherein the intermediate layer cell comprises: the device comprises a periodically repeated basic unit, two-side doped regions, two-side electrodes, a first isolation layer and a second isolation layer, wherein the periodically repeated basic unit comprises:
the second base region (20) is made of single crystal silicon material and has the thickness of less than 400 microns;
the fifth doped region (21) is made of a single crystal silicon material, and the fifth doped region (21) is manufactured on one side of the second base region (20) and has the same thickness as that of the second base region (20);
the sixth doped region (22) is made of a single crystal silicon material, the sixth doped region (22) is manufactured on the other side of the second base region (20), and the thickness of the sixth doped region is the same as that of the second base region (20);
two adjacent basic units are connected in series through a fifth doping area (21) and a sixth doping area (22);
the two doped regions are:
the seventh doped region (23) is made of a single crystal silicon material, and the seventh doped region (23) is manufactured at the outer side of the fifth doped region (21) of the basic unit at the outermost side and has the same thickness as that of the fifth doped region (21);
the eighth doped region (24) is made of a single crystal silicon material, and the eighth doped region (24) is manufactured at the outer side of the sixth doped region (22) of the basic unit at the other outermost side and has the same thickness as that of the sixth doped region (22);
the electrodes on both sides are:
the third electrode (25), the third electrode (25) is made on the lower surface of the seventh doped region (23), its width is smaller than the width of the seventh doped region (23);
the fourth electrode (26), the fourth electrode (26) is made on the lower surface of the eighth doped region (24), its width is smaller than the width of the eighth doped region (24);
the first isolation layer (27) is manufactured on the upper surface of the periodically repeated basic unit, covers the seventh doping area (23) and the eighth doping area (24), and the first isolation layer (27) is positioned on the lower surface of the periodically repeated basic unit of the top battery and covers the third doping area (13) and the fourth doping area (14) of the top battery;
and a second isolation layer (28) which is manufactured on the lower surface of the periodically repeated basic unit, covers the end parts of the seventh doping area (23) and the eighth doping area (24), and is connected with the third electrode (25) and the fourth electrode (26).
3. The vertical tandem solar cell of claim 1, wherein: wherein the bottom layer battery includes: the periodic repeated basic unit, the two-side doped region, the two-side electrode, the third isolation layer and the back reflection layer are divided into five parts, wherein the periodic repeated basic unit and the two-side doped region are located in the middle position of the lower surface of the second isolation layer (28) of the middle layer cell, the width of the periodic repeated basic unit and the two-side doped region is smaller than that of the second isolation layer (28), and the periodic repeated basic unit comprises:
the third base region (30) is a plurality of layers of black phosphorus materials, and the thickness of the third base region is from 2 layers to 1000 layers;
the ninth doped region (31) is made of a multi-layer black phosphorus material, the ninth doped region (31) is manufactured on one side of the third base region (30), and the thickness of the ninth doped region is the same as that of the third base region (30);
the tenth doping area (32) is made of a multi-layer black phosphorus material, the tenth doping area (32) is manufactured on the other side of the third base area (30), and the thickness of the tenth doping area is the same as that of the third base area (30);
two adjacent basic units are connected in series through a ninth doped region (31) and a tenth doped region (32);
the two doped regions are:
the eleventh doped region (33) is made of a multi-layer black phosphorus material, and the thickness of the eleventh doped region (33) is the same as that of the ninth doped region (31) of the basic unit at the outermost side;
the twelfth doped region (34) is made of a multi-layer black phosphorus material, the twelfth doped region (34) is manufactured at the outer side of the tenth doped region (32) of the other outermost basic unit, and the thickness of the twelfth doped region is the same as that of the tenth doped region (32);
the electrodes on both sides are:
the fifth electrode (35), the fifth electrode (35) is made on the lower surface of the eleventh doped region (33), its width is smaller than the width of the eleventh doped region (33);
the sixth electrode (36), the sixth electrode (36) is made on the lower surface of the twelfth doped region (34), its width is smaller than the width of the twelfth doped region (34);
a third isolation layer (37), wherein the third isolation layer (37) is manufactured on the lower surface of the periodically repeated basic unit, covers the end parts of the eleventh doping area (33) and the twelfth doping area (34), and is connected with the fifth electrode (35) and the sixth electrode (36);
and a back reflection layer (38), wherein the back reflection layer (38) is formed on the lower surface of the third isolation layer (37), covers the third isolation layer (37), and is connected with the fifth electrode (35) and the sixth electrode (36).
4. A vertical tandem solar cell according to any of claims 1, 2 and 3, wherein: wherein the antireflection layer (17), the first isolation layer (27), the second isolation layer (28) and the third isolation layer (37) are made of SiC, AlN or Al2O3、SiO2And SiNx or their combination, and the thickness of the back reflecting layer (38) is less than 2000 nm, and the thickness of the back reflecting layer is aluminum or silver and less than 2000 nm.
5. The vertical tandem solar cell of claim 1, wherein: the first base region (10) of the top layer cell is intrinsic semiconductor or P-type doped or N-type doped, the doping types of the first doping region (11) and the third doping region (13) are the same and are N-type or P-type doped, the doping concentration of the third doping region (13) is greater than that of the first doping region (11), and the doping concentration of the first doping region (11) is greater than that of the first base region (10); the doping types of the second doping area (12) and the fourth doping area (14) are the same, the doping types are N-type or P-type doping, the doping types of the second doping area (12) and the fourth doping area (14) are opposite to those of the first doping area (11) and the third doping area (13), the doping concentration of the fourth doping area (14) is larger than that of the second doping area (12), and the doping concentration of the second doping area (12) is larger than that of the first base area (10).
6. The vertical tandem solar cell of claim 2, wherein: the second base region (20) of the middle layer cell is intrinsic semiconductor or P-type doped or N-type doped, the doping types of the fifth doping region (21) and the seventh doping region (23) are the same and are N-type or P-type doped, the doping concentration of the seventh doping region (23) is greater than that of the fifth doping region (21), and the doping concentration of the fifth doping region (21) is greater than that of the second base region (20); the doping types of the sixth doping area (22) and the eighth doping area (24) are the same, the doping types are N-type or P-type doping, the doping types of the fifth doping area (21) and the seventh doping area (23) are opposite, the doping concentration of the eighth doping area (24) is larger than that of the sixth doping area (22), and the doping concentration of the sixth doping area (22) is larger than that of the second base area (20).
7. A vertical tandem solar cell according to claim 3, wherein: the third base region (30) of the bottom layer cell is intrinsic semiconductor or P-type doped or N-type doped, the doping types of the ninth doped region (31) and the eleventh doped region (33) are the same and are N-type or P-type doped, the doping concentration of the eleventh doped region (33) is greater than that of the ninth doped region (31), and the doping concentration of the ninth doped region (31) is greater than that of the third base region (30); the doping types of the tenth doping area (32) and the twelfth doping area (34) are the same, the tenth doping area is doped in an N type or a P type, the doping types of the ninth doping area (31) and the eleventh doping area (33) are opposite, the doping concentration of the twelfth doping area (34) is larger than that of the tenth doping area (32), and the doping concentration of the tenth doping area (32) is larger than that of the third base area (30).
8. A method of manufacturing a vertical tandem solar cell according to any one of claims 1 to 7, wherein: the method comprises the following steps:
step 1: preparing a second base region (20), a fifth doping region (21), a sixth doping region (22), seventh doping regions (23) and eighth doping regions (24) on two sides, a first isolation layer (27) and a second isolation layer (28) of the periodically repeated basic unit of the middle layer cell;
step 2: preparing a first base region (10), a first doping region (11), a second doping region (12), third doping regions (13) and fourth doping regions (14) on two sides and an antireflection film (17) of a periodically repeated basic unit of a top layer cell on the upper surface of the middle layer cell;
and step 3: preparing a third base region (30), a ninth doped region (31), a tenth doped region (32), eleventh doped regions (33) and twelfth doped regions (34) on two sides, a third isolation layer (37) and a back reflection layer (38) of a periodically repeated basic unit of the bottom layer cell in the middle of the lower surface of the middle layer cell;
and 4, step 4: preparing a first electrode (15) on the upper surface of the third doped region (13), preparing a second electrode (16) on the upper surface of the fourth doped region (14), preparing a third electrode (25) on the lower surface of the seventh doped region (23), preparing a fourth electrode (26) on the lower surface of the eighth doped region (24), preparing a fifth electrode (35) on the lower surface of the eleventh doped region (33), and preparing a sixth electrode (36) on the lower surface of the twelfth doped region (34).
9. The method of claim 8, wherein the method comprises: wherein the step 1 comprises the following steps:
step 1-1: the preparation of the basic substrate is completed by doping one surface of the monocrystalline silicon substrate to form a fifth doped region (21) in the area near the surface of the monocrystalline silicon substrate, doping the other surface of the monocrystalline silicon substrate to form a sixth doped region (22) in the area near the surface of the monocrystalline silicon substrate, and forming a second base region (20) in the undoped middle area of the monocrystalline silicon substrate;
step 1-2: preparing a seventh doped region (23) on the surface of a fifth doped region (21) of a basic substrate by using an epitaxial process to finish the preparation of the first outer substrate;
step 1-3: preparing an eighth doped region (24) on the surface of the sixth doped region (22) of the other basic substrate by using an epitaxial process to finish the preparation of the second outer substrate;
step 1-4: stacking a plurality of base substrates in this order in which a fifth doped region (21) of one base substrate is contiguous with a sixth doped region (22) of another base substrate, placing a first outer substrate on the uppermost portion of the stacked base substrates, and placing a second outer substrate on the lowermost portion of the stacked base substrates, said fifth doped regions (21) of all said substrates being on top and the sixth doped regions (22) being on bottom;
step 1-5: putting the stacked substrates into a key and pressing machine, and heating and pressing the keys to ensure that the adjacent substrate keys are combined together to finally form a whole;
step 1-6: cutting the keys in sequence along the direction vertical to the surface of the substrate to form an integral substrate, and preparing a series of flaky rectangular vertical structures consisting of a plurality of periodically repeated basic units and two side doped regions;
step 1-7: etching off the damage layer on the surface of the vertical structure by using a mixed solution of nitric acid and hydrofluoric acid;
step 1-8: a first isolation layer (27) and a second isolation layer (28) are respectively prepared on both surfaces of the vertical structure.
10. The method of claim 8, wherein the method comprises: wherein the step 2 comprises the following steps:
step 2-1: preparing a single layer or multiple layers of tungsten disulfide on the surface of the first isolation layer (27);
step 2-2: a first base region (10), a first doping region (11), a second doping region (12) and third doping regions (13) and fourth doping regions (14) on two sides of a periodically repeated basic unit are prepared on a single layer or multiple layers of tungsten disulfide through a doping method.
11. The method of claim 8, wherein the method comprises: wherein the step 3 comprises the following steps:
step 3-1: preparing a plurality of layers of black phosphorus on the surface of the second isolation layer (28);
step 3-2: preparing a third base region (30), a ninth doping region (31), a tenth doping region (32) and eleventh doping regions (33) and twelfth doping regions (34) on two sides of the third base region, the ninth doping region and the tenth doping region of the basic unit which are repeated periodically on the multiple layers of black phosphorus through a doping method;
step 3-3: preparing a third isolation layer (37) on the surface of the periodically repeated basic unit, wherein the third isolation layer (37) covers the end parts of the eleventh doping area (33) and the twelfth doping area (34);
step 3-4: a back reflection layer (38) is formed on the surface of the third isolation layer (37).
12. The method of claim 9, wherein the method comprises: and the epitaxy in the steps 1-2 and 1-3 is a method of laser rapid annealing after atmospheric epitaxy or magnetron sputtering of an amorphous silicon thin film.
13. The method of claim 9, wherein the method comprises: the first isolation layer (27) and the second isolation layer (28) prepared in the steps 1-8 are prepared by adopting a thermal oxidation method, a chemical vapor deposition method, a magnetron sputtering method, an ion beam sputtering method, a spraying method or a spin coating method.
14. The method of claim 10, wherein the method comprises: wherein, the step 2-1 and the step 3-1 adopt methods of electron beam evaporation, thermal evaporation, magnetron sputtering, chemical vapor deposition, chemical plating, metal organic chemical vapor deposition or transfer printing.
15. The method of claim 10, wherein the method comprises forming a vertical stack solar cellIs characterized in that: wherein the N-type doping formed in the step 2-2 is Cl2、CH2Cl2Or CHCl3A method for performing reactive ion etching on the surface of the single-layer or multi-layer tungsten disulfide by one or a combination of gases; the P-type doping is formed by ion implantation of niobium atoms.
16. The method of claim 11, wherein the method comprises: the N-type doping formed in the step 3-2 is formed by adopting a thermal diffusion method, and a diffusion source is trimethylaluminum; the P-type doping is formed by ion implantation of selenium atoms.
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