CN112186084A - Preparation method of GaAs/Si composite substrate, composite substrate and solar cell - Google Patents
Preparation method of GaAs/Si composite substrate, composite substrate and solar cell Download PDFInfo
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- CN112186084A CN112186084A CN201910591457.7A CN201910591457A CN112186084A CN 112186084 A CN112186084 A CN 112186084A CN 201910591457 A CN201910591457 A CN 201910591457A CN 112186084 A CN112186084 A CN 112186084A
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- 239000000758 substrate Substances 0.000 title claims abstract description 111
- 229910001218 Gallium arsenide Inorganic materials 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000005530 etching Methods 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 22
- 239000010703 silicon Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- -1 hydrogen ions Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000007639 printing Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 10
- 238000005240 physical vapour deposition Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000003486 chemical etching Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/20—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular shape, e.g. curved or truncated substrate
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Abstract
The invention belongs to the field of solar cells, and particularly relates to a preparation method of a GaAs/Si composite substrate structure, a composite substrate and a solar cell, wherein one surface of the GaAs substrate is processed to form a plurality of sawteeth, and a metal catalyst layer is evaporated on the surfaces of the sawteeth; and in an etching solution, stamping one surface of the GaAs substrate with the saw teeth onto the surface of the silicon substrate, and etching until the metal catalyst layer is removed by reaction and the surface of the silicon substrate forms a shape matched with the saw teeth on the GaAs substrate. The longitudinal section of the sawtooth is triangular, the sawtooth is beneficial to cutting into the lower substrate in the imprinting process, printing and etching are carried out simultaneously, the metal catalyst is removed along with reaction, metal cannot remain in the substrate, the upper sawtooth and the lower sawtooth in the formed composite substrate are completely matched, and the problem of lattice mismatch is favorably minimized.
Description
Technical Field
The invention belongs to the field of solar cells, and particularly relates to a structure of a triangle embedded GaAs/Si substrate and a preparation method thereof.
Background
The GaAs solar cell is a solar cell with higher conversion efficiency in III-V group semiconductors, has the advantages of high temperature resistance, strong radiation resistance, good temperature characteristic, suitability for light condensation and the like, and is receiving more and more extensive attention. With the continuous progress of the growth technology of group iii-v compound semiconductors, GaAs solar cells of high crystal quality are mainly prepared by epitaxial deposition in Metal Organic Chemical Vapor Deposition (MOCVD) or Molecular Beam Epitaxy (MBE). The unijunction GaAs solar cell generally comprises a substrate, a back field layer, a base layer, an emitting layer, a window layer and a contact layer, and the highest conversion efficiency reaches 28.6 percent at present. The global energy supply of solar cells is about 1%, a large amount of energy is wasted, and the solar cells are difficult to enter the civil market due to high price.
The most significant cost of solar cells comes from the substrate, hi-v GaAs or InP substrates are generally thicker and more expensive to ensure the desired growth of the cell, and since Si substrates are less expensive and more rigid, the transition from GaAs substrates to GaAs/Si substrates has been considered in the prior art, which can be more than half as expensive. However, lattice constants of the GaAs and Si substrates are not matched, so that a large stress is generated at an interface between the GaAs and Si, and during the process of continuing to grow the cell on the substrate under a high temperature condition, since the stress easily causes warpage of the substrate, the quality of a cell film further grown on the interface may be poor. In order to solve the above problems, the method used in the prior art is to add a gradually-changing buffer layer between the GaAs and the Si substrate, but the added buffer layer is generally thick, and also consumes a large amount of materials and cost, which is not suitable for large-scale industrial popularization.
Disclosure of Invention
Aiming at the problems of high cost and poor lattice matching of the composite substrate structure in the prior art, the invention provides a preparation method of a GaAs/Si composite substrate structure, which comprises the following steps:
processing one surface of a GaAs substrate to form a plurality of sawteeth, and evaporating a metal catalyst layer on the surface of the sawteeth;
and in an etching solution, stamping one surface of the GaAs substrate with the saw teeth onto the surface of the silicon substrate, and etching until the metal catalyst layer is removed by reaction and the surface of the silicon substrate forms a shape matched with the saw teeth on the GaAs substrate.
The invention adopts metal auxiliary chemical corrosion, the sawtooth shape is beneficial to cutting into the lower substrate in the imprinting process, the printing and the etching are carried out simultaneously, the metal catalyst is removed along with the reaction, the metal can not be left in the substrate, the upper sawtooth shape and the lower sawtooth shape in the composite substrate formed by the method are completely matched, and the problem of lattice mismatch is favorably reduced to the minimum.
Preferably, at least one longitudinal section of the top end of the sawtooth is triangular, and at least one longitudinal section of the top end of the sawtooth is triangular, so that the GaAs substrate on the upper layer can more easily enter the silicon substrate on the lower layer in the stamping and etching process.
Preferably, the saw teeth are triangular saw teeth, conical saw teeth or polyhedral pyramid-shaped. At least one longitudinal section of the triangular saw-tooth shape is triangular, and the other longitudinal section is rectangular.
Preferably, the etching solution contains strong acid and strong oxidant; the concentration of hydrogen ions in the etching liquid is 0.1-0.3 mol/L, and/or the strong oxidant is one or more of peroxide, potassium dichromate, potassium permanganate or oxysalt.
Preferably, the strong acid is HF and the strong oxidant is KMnO4The concentration of HF acid in the etching solution is 20-25mol/L, and the concentration of the strong oxidant is 0.5-0.8 g/L.
Preferably, the metal in the metal catalyst layer is one or more of Al, Cu, Ni, Ag, Au or Pt.
Preferably, the thickness of the metal catalyst layer is 50-100 nm.
Preferably, the specific operating parameters of the imprinting etching are that the pressure is 0.5-1 Pa, and the etching speed is 130-150 nm/min.
Preferably, when the longitudinal section is triangular, the vertex angle of the triangle is 30-90 degrees, and/or the height of the longitudinal section of the sawtooth is 50-70 um.
Preferably, the method of the present invention further comprises an operation of placing the etched composite substrate in an oven for drying.
Preferably, the drying is carried out in a vacuum oven at a temperature of 80-100 deg.C, N2The purity of the product is 99.999 percent, the pressure is 0.4-0.6 MPa, the heating rate is 8 ℃/min, and the time is 4-6 h. Under the above conditions, the sawtooth-shaped structure formed is more favorably and closely matched.
Preferably, the strength isThe acid is HF, and the strong oxidant is KMnO4The concentration of HF acid in the etching solution is 22-23 mol/L, and the concentration of the strong oxidant is 0.6-0.7 g/L. The metal in the metal catalyst layer is Ag, and the thickness of the metal catalyst layer is 40-60 nm. The specific operation parameters of the imprinting etching are that the control pressure is 0.7-0.9 Pa, and the etching speed is 130-150 nm/min. The angle of the triangular top end of the longitudinal section is 50-70 degrees, and the height of the longitudinal section of the sawtooth is 50-70 um.
The invention also aims to protect the GaAs/Si composite substrate structure prepared by the method.
Preferably, at least one longitudinal section of the top end of each saw tooth is triangular, and the vertex angle of each triangle is 60-90 degrees. The invention discovers that if the substrate is not completely removed in the use process of the battery, the substrate with the top angle is selected, the incident light can be reflected at the interface of the saw teeth and returns to the battery structure at the upper part of the substrate, the residence time of the light in the battery structure is prolonged, and the utilization rate of the battery to the light can be further improved.
Preferably, the ratio of the thickness of the silicon substrate removed in the zigzag shape to the thickness of the silicon substrate is 0.25 to 0.45: 1. The thickness can effectively reduce the cost of the substrate, and can realize no warping in the process of growing the battery, thereby ensuring the growth effect of the battery.
Preferably, the non-contact surfaces of the GaAs substrate and the silicon substrate are both planar.
A final object of the invention is to protect solar cells comprising the composite substrate structure according to the invention.
The invention has the following beneficial effects:
1) the method of the invention can make the GaAs and Si substrate form a completely fit structure, thus minimizing the problem of lattice mismatch and being beneficial to maintaining good performance of the cell in the process of continuously growing the cell.
2) The method has simple steps and simple and convenient operation, and is favorable for large-scale popularization and application.
Drawings
FIG. 1 is a GaAs and Si substrate structure prior to chemical etching;
fig. 2 is a GaAs and Si substrate structure after chemical etching.
In the figure: 10 is a GaAs substrate; 20 is a Si substrate; and 30 is a metal layer.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
The embodiment relates to a preparation method of a GaAs and Si composite substrate structure, which comprises the following steps (the process schematic diagram is shown in figure 1):
1) forming a plurality of triangular saw-shaped saw-teeth on one surface of the GaAs substrate by etching, wherein the angle of the top end of each triangle is 60 degrees, the height of the longitudinal section of each saw-tooth is 60 micrometers, and a layer of Ag material is evaporated on the surface of each saw-tooth by a PVD physical vapor deposition method, wherein the thickness of the Ag material is 50 nm; the height of the serrations was removed, at which time the GaAs substrate was 60um thick.
2) Putting a 240um thick silicon substrate with a planar surface and the GaAs substrate in the step 1) into an etching solution, wherein the concentration of HF in the etching solution is 22.5mol/L and KMnO is adopted4The concentration of the metal catalyst layer is 0.6g/L, the surface of the GaAs substrate with the sawteeth, the surface of which is evaporated with the metal catalyst layer, is stamped on the surface of the silicon substrate, the pressure is controlled to be 0.8Pa in the stamping process, the etching speed is 140nm/min, and the metal catalyst layer is removed through reaction until the surface of the silicon substrate forms a shape matched with the sawteeth on the GaAs substrate.
3) Placing the substrate in an oven for drying at 90 ℃ and N2The purity of the product is 99.999 percent, the pressure is 0.5MPa, the heating rate is 8 ℃/min, and the time is 5 h. And cooling to obtain the product (the structure diagram is shown in figure 2).
Example 2
The embodiment relates to a preparation method of a GaAs and Si composite substrate structure, which comprises the following steps:
1) forming a plurality of quadrangular pyramid saw-teeth on one surface of a GaAs substrate by etching, wherein the vertex angle of a triangle of a quadrangular pyramid section is 70 degrees, the height of a longitudinal section of each saw-tooth is 60 microns, and a layer of Ag material is evaporated on the surface of each saw-tooth by a PVD physical vapor deposition method, wherein the thickness of the Ag material is 60 nm; the height of the serrations was removed, at which time the thickness of the GaAs substrate was 70 um.
2) And (2) placing the silicon substrate with the surface being a plane and the thickness being 240um and the GaAs substrate in the step 1) in an etching solution, wherein the concentration of HF in the etching solution is 22.5mol/L, and the concentration of KMnO4 is 0.6g/L, stamping the surface of the GaAs substrate with the saw teeth, of which the surface is evaporated with the metal catalyst layer, onto the surface of the silicon substrate, controlling the pressure to be 0.7Pa in the stamping process, and the etching rate to be 140nm/min, until the metal catalyst layer is removed by reaction and the surface of the silicon substrate forms a shape matched with the saw teeth on the GaAs substrate.
3) Placing the substrate in an oven for drying at the temperature of 80 ℃ and N2The purity of the product is 99.999 percent, the pressure is 0.6MPa, the heating rate is 8 ℃/min, and the time is 6 h. And then cooling to obtain the product.
Example 3
The embodiment relates to a preparation method of a GaAs and Si composite substrate structure, which comprises the following steps:
1) forming a plurality of conical saw-shaped teeth on one surface of a GaAs substrate through etching, wherein the angle of the triangular top end of the longitudinal section of each cone is 90 degrees, the height of the longitudinal section of each saw-shaped tooth is 60 microns, and an Ag material layer is deposited on the GaAs in the triangular saw-shaped teeth on the surface of each saw-shaped tooth through a PVD physical vapor deposition method, wherein the thickness of the Ag material layer is 80 nm; the height of the serrations was removed when the thickness of the plane of the GaAs substrate was 100 um.
2) Putting a 240um thick silicon substrate with a planar surface and the GaAs substrate in the step 1) into an etching solution, wherein the concentration of HF in the etching solution is 22.5mol/L and KMnO is adopted4The concentration of the metal catalyst layer is 0.6g/L, the surface of the GaAs substrate with the sawtooth, the surface of which is evaporated with the metal catalyst layer, is stamped on the surface of the silicon substrate, the pressure is controlled to be 0.7Pa in the stamping process, the etching speed is 140nm/min, and the metal catalyst layer is removed through reaction, and the surface of the silicon substrate is formed and is matched with the surface of the silicon substrateThe serrations on the GaAs substrate conform to the shape.
3) Placing the substrate in an oven for drying at 100 ℃ and N2The purity of the product is 99.999 percent, the pressure is 0.6MPa, the heating rate is 8 ℃/min, and the time is 4 h. And then cooling to obtain the product.
Comparative example 1
Compared with embodiment 1, the substrate of this embodiment is a simple GaAs substrate, and the thickness thereof is the same as that of the composite substrate of embodiment 1, and is 450 um.
Examples of the experiments
A solar cell was produced using the composite substrate produced in examples 1 to 3 as a substrate for a solar cell. Putting the prepared composite substrate into MOCVD equipment, adjusting the temperature to 780 ℃, the pressure to 80torr, the buffer layer material to be GaAs, the doping type to be Si, the doping concentration range to be 1E18 and the thickness to be 400 nm; the back field layer material is Al0.4Ga0.6As, the doping type is Si, the doping concentration is 4E18, and the thickness is 100 nm; the base layer is GaAs, the doping type is Si, the doping concentration is 2E18, and the thickness is 1000 nm; the emitting layer is made of AlGaAs, the doping type is C, the doping concentration is 2E18, and the thickness is 80 nm; the window layer (Al0.4Ga0.6) is 0.5In0.5P, the doping type is C, the doping concentration is 3E18, the thickness is 60nm, the contact layer material is GaAs, the doping type is C, the doping concentration is 1E19, and the thickness is 70 nm.
And (3) preparing the solar cell by taking the GaAs substrate described in the comparative example 1 as a substrate, sequentially preparing the composite structure same as that of the composite substrate on the substrate to obtain the solar cell with the same upper layer structure, performing 21 parallel experiments on each embodiment and the comparative example, counting the defect-free solar cells, and calculating the yield of the product.
The yield of the battery is calculated, and the result is as follows:
| example 1 | Example 2 | Example 3 | Comparative example 1 | |
| Absorbance of light | 95.2％ | 90.4％ | 95.2％ | 95.2％ |
As can be seen from the above examples and comparative examples, the composite substrate of the present invention has excellent performance, and the obtained battery has high yield and no obvious difference from a simple GaAs substrate.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a GaAs/Si composite substrate structure is characterized by comprising the following steps:
processing one surface of a GaAs substrate to form a plurality of sawteeth, and evaporating a metal catalyst layer on the surface of the sawteeth;
and in an etching solution, stamping one surface of the GaAs substrate with the saw teeth onto the surface of the silicon substrate, and etching until the metal catalyst layer is removed by reaction and the surface of the silicon substrate forms a shape matched with the saw teeth on the GaAs substrate.
2. The method of preparing a composite substrate structure of claim 1, wherein at least one longitudinal cross-section of the tips of the serrations is triangular.
3. The method of manufacturing a composite substrate structure according to claim 1 or 2, wherein the etching solution contains a strong acid and a strong oxidizer; the concentration of hydrogen ions in the etching liquid is 0.1-0.3 mol/L, and/or the strong oxidant is one or more of peroxide, potassium dichromate, potassium permanganate or oxysalt.
4. The method of claim 3, wherein the strong acid is HF and the strong oxidizer is KMnO4The concentration of HF acid in the etching solution is 20-25mol/L, and the concentration of the strong oxidant is 0.5-0.8 g/L.
5. The method for preparing a composite substrate structure according to any one of claims 1 to 4, wherein the metal in the metal catalyst layer is one or more of Al, Cu, Ni, Ag, Au or Pt, and/or the thickness of the metal catalyst layer is 50 to 100 nm.
6. The method for preparing the composite substrate structure according to claim 5, wherein the specific operation parameters of the imprint etching are a pressure of 0.5-1 Pa and an etching rate of 130-150 nm/min.
7. A method of preparing a composite substrate structure according to any of claims 2 to 6, wherein when the longitudinal cross-section is triangular, the apex angle of the triangle is 30 to 90 ° and/or the height of the longitudinal cross-section of the serrations is 50 to 70 μm.
8. A GaAs/Si composite substrate structure, characterized by being prepared by the method of any one of claims 1 to 7.
9. The composite substrate structure according to claim 8, wherein at least one longitudinal section of the tips of the serrations is a triangle having a vertex angle of 60-90 °, and/or the ratio of the thickness of the silicon substrate excluding the serrations to the thickness of the silicon substrate is 0.25-0.45: 1.
10. A solar cell comprising the GaAs/Si composite substrate structure of claim 8 or 9. .
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113013300A (en) * | 2021-05-25 | 2021-06-22 | 北京芯海视界三维科技有限公司 | Light emitting device and display device |
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