CN108417719A - A kind of silicon substrate nucleocapsid photovoltaic cell and preparation method thereof - Google Patents
A kind of silicon substrate nucleocapsid photovoltaic cell and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of silicon substrate nucleocapsid photovoltaic cells and preparation method thereof, and this approach includes the following steps：Silicon nanowire array, the preparation of the first interface-modifying layer, the preparation of second contact surface decorative layer, the first PEDOT are prepared in the upper surface of monocrystalline silicon piece:The preparation of PSS layer, the 2nd PEDOT:The preparation of PSS layer, in the 2nd PEDOT:Whole surface hot evaporation metallic silver, the preparation of positive gate electrode and the preparation of backplate of PSS layer.By improving the structure and preparation process of silicon substrate nucleocapsid photovoltaic cell, the photoelectric conversion efficiency of the silicon substrate nucleocapsid photovoltaic cell of the present invention is effectively increased.
Description
Technical field
The present invention relates to photovoltaic cell technical fields, more particularly to a kind of silicon substrate nucleocapsid photovoltaic cell and its preparation
Method.
Background technology
In the preparation process of existing organic inorganic hybridization photovoltaic cell, typically first with metal catalytic chemical attack
Method prepares silicon nanowire array on n-type silicon chip surface, then carries out the processing that methylates to n-type silicon chip, forms Si-CH3Key is with blunt
SiClx surface, then in the positive spin coating PEDOT of n-type silicon chip:PSS solution is simultaneously made annealing treatment to form PEDOT：PSS layer,
Then silver-colored gate electrode is deposited in n-type silicon chip front and backplate is deposited at the n-type silicon chip back side, to form conventional organic-inorganic
Hybrid photovoltaic cells.In existing organic inorganic hybridization photovoltaic cell, n-type silicon chip and PEDOT：Contact interface between PSS layer
Defect state is more, causes electrons and holes to occur compound, and then cause its photoelectric conversion efficiency relatively low.
Invention content
The purpose of the present invention is overcoming above-mentioned the deficiencies in the prior art, provide a kind of silicon substrate nucleocapsid photovoltaic cell and its
Preparation method.
To achieve the above object, the preparation method of a kind of silicon substrate nucleocapsid photovoltaic cell proposed by the present invention, including with
Lower step：
(1) silicon nanowire array is prepared in the upper surface of monocrystalline silicon piece, is then impregnated in HF solution to remove the silicon
The natural silicon oxide on the surface of single silicon nanowires in nano-wire array；
The preparation of (2) first interface-modifying layers：Contain isobutanol in the upper surface spin coating for the monocrystalline silicon piece that step (1) obtains
First mixed solution of hafnium and P3HT, wherein in first mixed solution isobutanol hafnium a concentration of 0.3-0.5mg/ml,
The rotating speed of a concentration of 1-1.5mg/ml of P3HT, spin coating are 5500-6000 revs/min, then carry out first time annealing, shape
At first interface-modifying layer；
(3) preparation of second contact surface decorative layer：Contain isobutanol in the upper surface spin coating for the monocrystalline silicon piece that step (2) obtains
Second mixed solution of hafnium and P3HT, wherein in second mixed solution isobutanol hafnium a concentration of 0.1-0.2mg/ml,
The rotating speed of a concentration of 1.5-2mg/ml of P3HT, spin coating are 5000-5500 revs/min, then carry out second and make annealing treatment, shape
At the second contact surface decorative layer；
(4) the first PEDOT:The preparation of PSS layer：In the upper surface spin coating PEDOT for the monocrystalline silicon piece that step (3) obtains:PSS
The rotating speed of solution, spin coating is 4000-5000 revs/min, then carries out third time annealing, forms the first PEDOT:
PSS layer；
(5) the 2nd PEDOT:The preparation of PSS layer：Contain silver in the upper surface spin coating for the monocrystalline silicon piece that step (4) obtains to receive
The PEDOT of rice grain and black phosphorus alkene:The rotating speed of PSS solution, spin coating is 3000-4000 revs/min, then carries out the 4th annealing
Processing forms the 2nd PEDOT:PSS layer；
(6) in the 2nd PEDOT:The whole surface hot evaporation metallic silver of PSS layer, wherein the speed of hot evaporation metallic silver
Rate is 0.5-2 angstroms of meter per second, and the time of each evaporation metal silver is 3-6 seconds；
(7) preparation of positive gate electrode；
(8) preparation of backplate.
Preferably, in the step (1), the length of the single silicon nanowires in the silicon nanowire array is 1-2
Micron, a diameter of 300-500 nanometers of the single silicon nanowires, the spacing of adjacent silicon nanowires is 500-800 nanometers.
Preferably, in the step (2) and the step (3), the first time makes annealing treatment and described second
The annealing temperature of annealing is 140-160 DEG C, and the annealing time of first time annealing is 20-30 minutes, described the
The annealing time of double annealing processing is 10-20 minutes.
Preferably, in the step (4), the annealing temperature of the third time annealing is 100-110 DEG C, described
The annealing time of third time annealing is 15-25 minutes, the first PEDOT:The thickness of PSS layer is 20-40 nanometers.
Preferably, in the step (5), the annealing temperature of the 4th annealing is 110-120 DEG C, described
The annealing time of third time annealing is 10-20 minutes, the 2nd PEDOT:The thickness of PSS layer is 30-60 nanometers.
Preferably, the grain size of the silver nano-grain is 5-10 nanometers.
Preferably, in the step (7), the positive gate electrode, the front are formed by hot evaporation metallic silver
The thickness of gate electrode is 200-300 nanometers.
Preferably, forming the backplate, the backplate by hot evaporation metallic aluminium in the step (8)
Thickness be 300-400 nanometers.
The present invention also provides a kind of silicon substrate nucleocapsid photovoltaic cell, the silicon substrate nucleocapsid photovoltaic cell is
The silicon substrate nucleocapsid photovoltaic cell to be formed is prepared using the above method.
The present invention has following advantages compared with prior art：
In the silicon substrate nucleocapsid photovoltaic cell of the present invention, by silicon nanowires and the first PEDOT:Shape between PSS layer
At two interface-modifying layers silicon on the one hand can be effectively reduced by optimizing the specific preparation process and parameter of interface-modifying layer
The defect state of nanowire surface, on the other hand improves silicon nanowires and PEDOT:The contact quality of PSS layer forms good
Schottky junction effectively reduces electronics and dies out in the compound of interface with hole, is conducive to the separation and transmission of electrons and holes, has
Effect improves the open-circuit voltage and fill factor of photovoltaic cell, while the 2nd PEDOT:Contain silver nano-grain and black in PSS layer
Phosphorus alkene, and in the 2nd PEDOT:The whole surface hot evaporation of PSS layer has metallic silver, effectively increases the migration rate in hole, into
One step improves the photoelectric conversion efficiency of photovoltaic cell.The preparation method of the silicon substrate nucleocapsid photovoltaic cell of the present invention is simply easy
Row, and the temperature of each annealing operation is relatively low, effectively reduces manufacturing cost, and during preparing each layer using solwution method,
By the concrete content for optimizing each component and specific preparation technology parameter, silicon substrate nucleocapsid photovoltaic cell is effectively increased
Photoelectric conversion efficiency.
Description of the drawings
Fig. 1 is the structural schematic diagram of the silicon substrate nucleocapsid photovoltaic cell of the present invention.
Specific implementation mode
A kind of preparation method for silicon substrate nucleocapsid photovoltaic cell that the specific embodiment of the invention proposes, including following step
Suddenly：
(1) silicon nanowire array is prepared in the upper surface of n type single crystal silicon piece, is then impregnated in HF solution described to remove
The natural silicon oxide on the surface of single silicon nanowires in silicon nanowire array；
The preparation of (2) first interface-modifying layers：Contain in the upper surface spin coating for the n type single crystal silicon piece that step (1) obtains different
First mixed solution of butanol hafnium and P3HT, wherein in first mixed solution isobutanol hafnium a concentration of 0.3-0.5mg/
The rotating speed of a concentration of 1-1.5mg/ml of ml, P3HT, spin coating are 5500-6000 revs/min, are then carried out at first time annealing
Reason forms first interface-modifying layer；
(3) preparation of second contact surface decorative layer：Contain in the upper surface spin coating for the n type single crystal silicon piece that step (2) obtains different
Second mixed solution of butanol hafnium and P3HT, wherein in second mixed solution isobutanol hafnium a concentration of 0.1-0.2mg/
The rotating speed of a concentration of 1.5-2mg/ml of ml, P3HT, spin coating are 5000-5500 revs/min, are then carried out at second of annealing
Reason, forms the second contact surface decorative layer；
(4) the first PEDOT:The preparation of PSS layer：In the upper surface spin coating PEDOT for the n type single crystal silicon piece that step (3) obtains:
The rotating speed of PSS solution, spin coating is 4000-5000 revs/min, then carries out third time annealing, forms described first
PEDOT:PSS layer；
(5) the 2nd PEDOT:The preparation of PSS layer：Contain silver in the upper surface spin coating for the n type single crystal silicon piece that step (4) obtains
The PEDOT of nano particle and black phosphorus alkene:The rotating speed of PSS solution, spin coating is 3000-4000 revs/min, then move back for the 4th time
Fire processing, forms the 2nd PEDOT:PSS layer；
(6) in the 2nd PEDOT:The whole surface hot evaporation metallic silver of PSS layer, wherein the speed of hot evaporation metallic silver
Rate is 0.5-2 angstroms of meter per second, and the time of each evaporation metal silver is 3-6 seconds；
(7) preparation of positive gate electrode；
(8) preparation of backplate.
Wherein, in the step (1), the length of the single silicon nanowires in the silicon nanowire array is 1-2 microns,
The spacing of a diameter of 300-500 nanometers of the single silicon nanowires, adjacent silicon nanowires is 500-800 nanometers.In the step
Suddenly in (2) and the step (3), the annealing temperature of the first time annealing and second of annealing is 140-
160 DEG C, the annealing time of the first time annealing is 20-30 minutes, and the annealing time of second of annealing is
10-20 minutes.In the step (4), the annealing temperature of the third time annealing is 100-110 DEG C, the third time
The annealing time of annealing is 15-25 minutes, the first PEDOT:The thickness of PSS layer is 20-40 nanometers.In the step
(5) in, the annealing temperature of the 4th annealing is 110-120 DEG C, and the annealing time of the third time annealing is
10-20 minutes, the 2nd PEDOT:The thickness of PSS layer is 30-60 nanometers.The grain size of the silver nano-grain is received for 5-10
Rice.In the step (7), the positive gate electrode is formed by hot evaporation metallic silver, the thickness of the positive gate electrode is
200-300 nanometers.The backplate, the thickness of the backplate are formed by hot evaporation metallic aluminium in the step (8)
Degree is 300-400 nanometers.
As shown in Figure 1, the silicon substrate nucleocapsid photovoltaic cell that the present invention is prepared according to the above method, the silicon substrate nucleocapsid knot
Structure photovoltaic cell includes backplate 1, n type single crystal silicon piece 2, silicon nanowire array 3, the first interface-modifying layer 4, the from bottom to up
Second interface decorative layer 5, the first PEDOT:PSS layer 6, the 2nd PEDOT:PSS layer 7 and positive gate electrode 8.
Embodiment 1：
A kind of preparation method of silicon substrate nucleocapsid photovoltaic cell, includes the following steps：
(1) silicon nanowire array is prepared in the upper surface of n type single crystal silicon piece, is then impregnated in HF solution described to remove
The natural silicon oxide on the surface of single silicon nanowires in silicon nanowire array；
The preparation of (2) first interface-modifying layers：Contain in the upper surface spin coating for the n type single crystal silicon piece that step (1) obtains different
First mixed solution of butanol hafnium and P3HT, wherein in first mixed solution isobutanol hafnium a concentration of 0.4mg/ml,
The rotating speed of a concentration of 1.2mg/ml of P3HT, spin coating are 5800 revs/min, then progress first time annealing, described in formation
First interface-modifying layer；
(3) preparation of second contact surface decorative layer：Contain in the upper surface spin coating for the n type single crystal silicon piece that step (2) obtains different
Second mixed solution of butanol hafnium and P3HT, wherein in second mixed solution isobutanol hafnium a concentration of 0.15mg/ml,
The rotating speed of a concentration of 1.8mg/ml of P3HT, spin coating are 5200 revs/min, then carry out second and make annealing treatment, described in formation
Second contact surface decorative layer；
(4) the first PEDOT:The preparation of PSS layer：In the upper surface spin coating PEDOT for the n type single crystal silicon piece that step (3) obtains:
The rotating speed of PSS solution, spin coating is 4500 revs/min, then carries out third time annealing, forms the first PEDOT:PSS
Layer；
(5) the 2nd PEDOT:The preparation of PSS layer：Contain silver in the upper surface spin coating for the n type single crystal silicon piece that step (4) obtains
The PEDOT of nano particle and black phosphorus alkene:The rotating speed of PSS solution, spin coating is 3500 revs/min, is then carried out at the 4th annealing
Reason forms the 2nd PEDOT:PSS layer；
(6) in the 2nd PEDOT:The whole surface hot evaporation metallic silver of PSS layer, wherein the speed of hot evaporation metallic silver
Rate is 1 angstrom of meter per second, and the time of each evaporation metal silver is 5 seconds；
(7) preparation of positive gate electrode；
(8) preparation of backplate.
Wherein, in the step (1), the length of the single silicon nanowires in the silicon nanowire array is 1.5 microns,
The spacing of a diameter of 400 nanometers of the single silicon nanowires, adjacent silicon nanowires is 600 nanometers.In the step (2) and institute
It states in step (3), the annealing temperature of first time annealing and second of annealing is 150 DEG C, described first
The annealing time of secondary annealing is 25 minutes, and the annealing time of second of annealing is 15 minutes.In the step
(4) in, the annealing temperature of the third time annealing is 105 DEG C, and the annealing time of the third time annealing is 20 points
Clock, the first PEDOT:The thickness of PSS layer is 30 nanometers.In the step (5), the annealing of the 4th annealing
Temperature is 115 DEG C, and the annealing time of the third time annealing is 15 minutes, the 2nd PEDOT:The thickness of PSS layer is
40 nanometers.The grain size of the silver nano-grain is 8 nanometers.In the step (7), by hot evaporation metallic silver formed it is described just
The thickness of face gate electrode, the positive gate electrode is 220 nanometers.Institute is formed by hot evaporation metallic aluminium in the step (8)
Backplate is stated, the thickness of the backplate is 350 nanometers.
The open-circuit voltage of silicon substrate nucleocapsid photovoltaic cell prepared by the above method is 0.6V, short circuit current 35.3mA/
cm2, fill factor 0.73, photoelectric conversion efficiency 15.5%.
Embodiment 2
A kind of preparation method of silicon substrate nucleocapsid photovoltaic cell, includes the following steps：
(1) silicon nanowire array is prepared in the upper surface of n type single crystal silicon piece, is then impregnated in HF solution described to remove
The natural silicon oxide on the surface of single silicon nanowires in silicon nanowire array；
The preparation of (2) first interface-modifying layers：Contain in the upper surface spin coating for the n type single crystal silicon piece that step (1) obtains different
First mixed solution of butanol hafnium and P3HT, wherein in first mixed solution isobutanol hafnium a concentration of 0.5mg/ml,
A concentration of 1mg/ml of P3HT, the rotating speed of spin coating are 6000 revs/min, then carry out first time annealing, form described the
One interface-modifying layer；
(3) preparation of second contact surface decorative layer：Contain in the upper surface spin coating for the n type single crystal silicon piece that step (2) obtains different
Second mixed solution of butanol hafnium and P3HT, wherein in second mixed solution isobutanol hafnium a concentration of 0.2mg/ml,
The rotating speed of a concentration of 1.5mg/ml of P3HT, spin coating are 5000 revs/min, then carry out second and make annealing treatment, described in formation
Second contact surface decorative layer；
(4) the first PEDOT:The preparation of PSS layer：In the upper surface spin coating PEDOT for the n type single crystal silicon piece that step (3) obtains:
The rotating speed of PSS solution, spin coating is 4000 revs/min, then carries out third time annealing, forms the first PEDOT:PSS
Layer；
(5) the 2nd PEDOT:The preparation of PSS layer：Contain silver in the upper surface spin coating for the n type single crystal silicon piece that step (4) obtains
The PEDOT of nano particle and black phosphorus alkene:The rotating speed of PSS solution, spin coating is 3000 revs/min, is then carried out at the 4th annealing
Reason forms the 2nd PEDOT:PSS layer；
(6) in the 2nd PEDOT:The whole surface hot evaporation metallic silver of PSS layer, wherein the speed of hot evaporation metallic silver
Rate is 2 angstroms of meter per seconds, and the time of each evaporation metal silver is 6 seconds；
(7) preparation of positive gate electrode；
(8) preparation of backplate.
Wherein, in the step (1), the length of the single silicon nanowires in the silicon nanowire array is 2 microns, institute
The spacing of state single silicon nanowires a diameter of 500 nanometers, adjacent silicon nanowires is 800 nanometers.In the step (2) and described
In step (3), the annealing temperature of the first time annealing and second of annealing is 140 DEG C, the first time
The annealing time of annealing is 30 minutes, and the annealing time of second of annealing is 20 minutes.In the step (4)
In, the annealing temperature of the third time annealing is 100 DEG C, and the annealing time of the third time annealing is 15 minutes,
First PEDOT:The thickness of PSS layer is 40 nanometers.In the step (5), the annealing temperature of the 4th annealing
Degree is 120 DEG C, and the annealing time of the third time annealing is 10 minutes, the 2nd PEDOT:The thickness of PSS layer is 50
Nanometer.The grain size of the silver nano-grain is 5 nanometers.In the step (7), the front is formed by hot evaporation metallic silver
The thickness of gate electrode, the positive gate electrode is 200 nanometers.It is formed by hot evaporation metallic aluminium in the step (8) described
The thickness of backplate, the backplate is 300 nanometers.
The open-circuit voltage of silicon substrate nucleocapsid photovoltaic cell prepared by the above method is 0.58V, short circuit current 34.8mA/
cm2, fill factor 0.74, photoelectric conversion efficiency 14.9%.
Comparative example：
Silicon substrate nucleocapsid photovoltaic cell in order to protrude the present invention has excellent photoelectric conversion efficiency, as a comparison,
A kind of preparation method of silicon substrate nucleocapsid photovoltaic cell, includes the following steps：(1) it is prepared in the upper surface of n type single crystal silicon piece
Silicon nanowire array；(3) processing that methylates on n-type silicon chip surface；(4)PEDOT:The preparation of PSS layer：In the n that step (3) obtains
The positive spin coating PEDOT of type silicon chip:PSS solution, is then made annealing treatment；(4) preparation of positive gate electrode；(5) back side electricity
The preparation of pole.Wherein, in the step (1) using metal catalytic chemical corrosion method silicon nanowires is prepared on n-type silicon chip surface
Array.In the step (2), the processing that methylates is carried out to n-type silicon chip, forms Si-CH3Key is to be passivated silicon face.Described
In step (3), the time of 120 DEG C of the temperature of the annealing, the annealing is 25 minutes.In the step (4),
The positive gate electrode is formed by thermal evaporation deposition, the positive gate electrode is silver-colored gate electrode, the thickness of the positive gate electrode
It is 150 nanometers.The backplate is formed by thermal evaporation deposition in the step (5), the material of the backplate is aluminium,
The thickness of the backplate is 250 nanometers.
The open-circuit voltage of silicon substrate nucleocapsid photovoltaic cell prepared by the above method is 0.56V, short circuit current 32.8mA/
cm2, fill factor 0.61, photoelectric conversion efficiency 11.2%.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (9)
1. a kind of preparation method of silicon substrate nucleocapsid photovoltaic cell, it is characterised in that：Include the following steps：
(1) silicon nanowire array is prepared in the upper surface of monocrystalline silicon piece, is then impregnated in HF solution to remove the silicon nanometer
The natural silicon oxide on the surface of single silicon nanowires in linear array；
The preparation of (2) first interface-modifying layers：The upper surface spin coating for the monocrystalline silicon piece that step (1) obtains contain isobutanol hafnium and
The first mixed solution of P3HT, wherein in first mixed solution isobutanol hafnium a concentration of 0.3-0.5mg/ml, P3HT's
The rotating speed of a concentration of 1-1.5mg/ml, spin coating are 5500-6000 revs/min, then progress first time annealing, described in formation
First interface-modifying layer；
(3) preparation of second contact surface decorative layer：The upper surface spin coating for the monocrystalline silicon piece that step (2) obtains contain isobutanol hafnium and
The second mixed solution of P3HT, wherein in second mixed solution isobutanol hafnium a concentration of 0.1-0.2mg/ml, P3HT's
The rotating speed of a concentration of 1.5-2mg/ml, spin coating are 5000-5500 revs/min, then carry out second and make annealing treatment, described in formation
Second contact surface decorative layer；
(4) the first PEDOT:The preparation of PSS layer：In the upper surface spin coating PEDOT for the monocrystalline silicon piece that step (3) obtains:PSS is molten
The rotating speed of liquid, spin coating is 4000-5000 revs/min, then carries out third time annealing, forms the first PEDOT:PSS
Layer；
(5) the 2nd PEDOT:The preparation of PSS layer：Contain silver nanoparticle in the upper surface spin coating for the monocrystalline silicon piece that step (4) obtains
The PEDOT of grain and black phosphorus alkene:The rotating speed of PSS solution, spin coating is 3000-4000 revs/min, is then carried out at the 4th annealing
Reason forms the 2nd PEDOT:PSS layer；
(6) in the 2nd PEDOT:The whole surface hot evaporation metallic silver of PSS layer, wherein the rate of hot evaporation metallic silver is equal
Time for 0.5-2 angstroms of meter per second, each evaporation metal silver is 3-6 seconds；
(7) preparation of positive gate electrode；
(8) preparation of backplate.
2. the preparation method of silicon substrate nuclear structure photovoltaic cell according to claim 1, it is characterised in that：In the step
(1) in, the length of the single silicon nanowires in the silicon nanowire array is 1-2 microns, the diameter of the single silicon nanowires
It it is 300-500 nanometers, the spacing of adjacent silicon nanowires is 500-800 nanometers.
3. the preparation method of silicon substrate nucleocapsid photovoltaic cell according to claim 1, it is characterised in that：In the step
(2) and in the step (3), the annealing temperature of the first time annealing and second of annealing is 140-160
DEG C, the annealing time of the first time annealing is 20-30 minutes, and the annealing time of second of annealing is 10-
20 minutes.
4. the preparation method of silicon substrate nucleocapsid photovoltaic cell according to claim 1, it is characterised in that：In the step
(4) in, the annealing temperature of the third time annealing is 100-110 DEG C, and the annealing time of the third time annealing is
15-25 minutes, the first PEDOT:The thickness of PSS layer is 20-40 nanometers.
5. the preparation method of silicon substrate nucleocapsid photovoltaic cell according to claim 1, it is characterised in that：In the step
(5) in, the annealing temperature of the 4th annealing is 110-120 DEG C, and the annealing time of the third time annealing is
10-20 minutes, the 2nd PEDOT:The thickness of PSS layer is 30-60 nanometers.
6. the preparation method of silicon substrate nucleocapsid photovoltaic cell according to claim 5, it is characterised in that：The silver nanoparticle
The grain size of particle is 5-10 nanometers.
7. the preparation method of silicon substrate nucleocapsid photovoltaic cell according to claim 1, it is characterised in that：In the step
(7) in, the positive gate electrode is formed by hot evaporation metallic silver, the thickness of the positive gate electrode is 200-300 nanometers.
8. the preparation method of silicon substrate nucleocapsid photovoltaic cell according to claim 1, it is characterised in that：In the step
(8) backplate is formed by hot evaporation metallic aluminium in, the thickness of the backplate is 300-400 nanometers.
9. a kind of silicon substrate nucleocapsid photovoltaic cell, which is characterized in that the silicon substrate nucleocapsid photovoltaic cell is using right
It is required that 1-8 any one of them methods prepare the silicon substrate nucleocapsid photovoltaic cell to be formed.
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| CN110931647A (en) * | 2019-12-05 | 2020-03-27 | 徐州顺意半导体科技有限公司 | Preparation method of solar cell |
| CN110993794A (en) * | 2019-11-22 | 2020-04-10 | 徐州吴瑞信息科技有限公司 | Heterojunction solar cell and preparation method thereof |
| CN111029433A (en) * | 2019-12-05 | 2020-04-17 | 徐州吴瑞信息科技有限公司 | Silicon-based heterojunction solar cell and preparation method thereof |
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