CN115810687A - Light absorption enhancement and antireflection structure for silicon substrate and preparation and test methods thereof - Google Patents
Light absorption enhancement and antireflection structure for silicon substrate and preparation and test methods thereof Download PDFInfo
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- CN115810687A CN115810687A CN202211516539.3A CN202211516539A CN115810687A CN 115810687 A CN115810687 A CN 115810687A CN 202211516539 A CN202211516539 A CN 202211516539A CN 115810687 A CN115810687 A CN 115810687A
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Abstract
The invention relates to a light absorption enhancement and antireflection structure for a silicon substrate and a preparation and test method thereof, wherein the light absorption enhancement and antireflection structure for the silicon substrate comprises the following components: the silicon substrate is provided with a silicon substrate, a semiconductor nano-pillar polymer periodic array positioned on the upper surface of the silicon substrate and a medium antireflection layer covering the upper surfaces of the semiconductor nano-pillars of the semiconductor nano-pillar polymer, and the semiconductor nano-pillar polymer periodic array is formed by periodically and uniformly distributing the semiconductor nano-pillar polymer. The invention can play the roles of light absorption enhancement and antireflection in a wider wave band.
Description
Technical Field
The invention relates to the field of antireflection in a silicon solar cell, in particular to a light absorption enhancement and antireflection structure for a silicon substrate and preparation and test methods thereof.
Background
Silicon solar cells are common solar cells, and have been used on a large scale. However, since the surface of the silicon substrate has high reflection to sunlight, light cannot enter the silicon solar cell, and the photoelectric conversion efficiency is greatly limited. Therefore, the key problem of improving the performance of the silicon solar cell is that the broadband increases the light absorption of the silicon substrate and reduces the surface reflection.
Conventionally, a multi-layer thin film structure composed of a dielectric can obtain a broadband antireflection effect, but the structure has a strict requirement on the refractive index of a film material. Due to the limited choice of materials, ideal antireflection effect is difficult to achieve by adopting a multilayer film structure.
In order to overcome the technical problems, typically, "Optical Impedance Matching Using Coupled plasma Nanoparticle Arrays" published in 2011, 11 th 1760-1765 by Nano Letters, et al, designs a composite structure of a dielectric antireflection layer and a metal Nanoparticle array on the surface of a silicon substrate. Researches show that the metal nanoparticles have strong scattering on incident light due to supporting local surface plasmon resonance, and scattered light preferentially enters a silicon substrate with higher refractive index. The surface reflection of the silicon substrate can be further reduced by utilizing the combined action of the antireflection effect of the medium antireflection layer and the forward scattering effect of the metal nano particles. However, the structure can only play a good role in antireflection in some specific wave bands, and the reflection of other wave bands (for example, 600-800nm wave bands) is still high. In addition, the metal material has larger absorption loss, so that the further absorption of the silicon substrate to light is limited, and further improvement of the photoelectric conversion efficiency of the silicon solar cell is limited.
Disclosure of Invention
The invention aims to solve the technical problems that a composite structure of a dielectric antireflection layer and a metal nanoparticle array only has good antireflection performance at a specific waveband, the reflection of other wavebands still needs to be further reduced, and a metal material has larger absorption loss and limits the further absorption of a silicon substrate to light, and provides a light absorption enhancement and antireflection structure for the silicon substrate, which can play a role in light absorption enhancement and antireflection at a wider waveband.
In order to solve the technical problem, the technical scheme of the invention is as follows: a light absorption enhancement and antireflection structure for a silicon substrate, comprising:
the semiconductor nano-pillar polymer periodic array is positioned on the upper surface of the silicon substrate and is formed by periodically and uniformly distributing semiconductor nano-pillar polymers;
and the dielectric antireflection layer is covered on the silicon substrate and the upper surface of the semiconductor nano column polymer.
Furthermore, the semiconductor nano-column is made of Si, gaAs or Ge.
Further, the semiconductor nano-pillar polymer is a semiconductor nano-pillar dimer, a semiconductor nano-pillar trimer or a semiconductor nano-pillar tetramer.
Further, the dielectric antireflection layer material is Si 3 N 4 Or SiO 2 Or TiO 2 。
Further, the thickness of the medium antireflection layer is 5 nm-100 nm.
The invention also provides a preparation method of the light absorption enhancement and antireflection structure for the silicon substrate, which comprises the following steps:
s1, preparing a periodic array consisting of semiconductor nano-pillar polymers on a silicon substrate;
and S2, preparing a dielectric antireflection layer on the upper surface of the silicon substrate and the upper surface of the semiconductor nano column polymer.
Further, in S1, in the case that the material of the semiconductor nanocolumn in the semiconductor nanocolumn multimer is Si, the preparation method of the semiconductor nanocolumn multimer is an electron beam exposure technique or a focused ion beam technique or a nanoimprint technique;
under the condition that the material of the semiconductor nano-pillar in the semiconductor nano-pillar polymer is Ge or GaAs, the preparation method of the semiconductor nano-pillar polymer comprises the following steps: firstly, preparing a semiconductor nano film on the upper surface of a silicon substrate by adopting an electron beam evaporation method, and then preparing a semiconductor nano column polymer on the semiconductor nano film by adopting an electron beam exposure technology or a focused ion beam technology or a nanoimprint technology.
Further, in S2, the preparation method of the dielectric antireflection layer is a chemical vapor deposition method or an electron beam evaporation method.
The invention also provides a test method for the light absorption enhancement and antireflection structure of the silicon substrate, which comprises the following steps of carrying out simulation calculation by using a time domain finite difference method: firstly, constructing a physical model of a periodic unit in a light absorption enhancement and antireflection structure for a silicon substrate; then setting a perfect matching layer on the upper and lower boundaries of the physical model, setting periodic boundary conditions on the peripheral boundaries, and setting a beam of plane waves which are vertically incident on the upper surface; and calculating the transmission spectrum and the reflection spectrum of the corresponding physical model.
After the technical scheme is adopted, the light absorption enhancement and antireflection structure for the silicon substrate can support a plurality of Mie resonances, and the characteristics of the Mie resonances, such as peak positions, bandwidth, local fields and the like, are influenced by the interference effect among the semiconductor nano columns in the semiconductor nano column polymer and the coupling effect between the semiconductor nano column polymer and the periodic array diffracted wave. By adjusting factors such as the size of the semiconductor nano-column, the gap and the distribution of polymers, the material and the thickness of a dielectric layer, the period of an array and the like, a plurality of Mie resonances with excellent performance can be obtained. The Mie resonances have obvious local field enhancement and lower absorption loss, and have strong scattering to incident light, and scattered light preferentially enters a silicon substrate with higher refractive index, so that the absorption of the silicon substrate to light is enhanced. The multiple Mie resonances enable light to enter the silicon substrate in multiple wave band ranges, and by combining the antireflection effect of the medium antireflection layer, the structure can achieve light absorption enhancement and antireflection effects on the silicon substrate in a wide wave band range, so that the performance of the silicon solar cell is improved, and the silicon solar cell is suitable for industrial production.
Drawings
FIG. 1 is a flow chart of the preparation of a light absorption enhancement and antireflective structure for a silicon substrate in example 1;
FIG. 2 is a flow chart illustrating the preparation of a structure in which an anti-reflective dielectric layer is combined with a periodic array of semiconductor nanopillars according to comparative example 1;
FIG. 3 is a graph of the reflection curves of the structure of example 1 and a bare silicon structure under the irradiation of normal incident light in a 400-1100nm band, which are calculated by using a time-domain finite difference method;
FIG. 4 is a graph of transmission curves of the structure of example 1 and a bare silicon structure under normal incident light irradiation in a 400-1100nm band calculated by using a finite difference time domain method;
FIG. 5 is a graph of transmission curves and reflection curves of the structure of comparative example 1 under the irradiation of normal incident light in the 400-1100nm band calculated by using a time-domain finite difference method;
in fig. 1 and 2, 1, a silicon substrate; 2. a periodic array of semiconducting nanopillar multimers; 3. a dielectric antireflective layer; 4. a periodic array of semiconductor nanopillars.
Detailed Description
In order that the manner in which the present invention is attained and can be understood in detail, a more particular description of the invention briefly summarized above may be had by reference to the embodiments thereof which are illustrated in the appended drawings.
As shown in fig. 1, a light absorption enhancement and antireflection structure for a silicon substrate includes:
the semiconductor nano-pillar polymer periodic array 2 is positioned on the upper surface of the silicon substrate 1, and the semiconductor nano-pillar polymer periodic array 2 is formed by periodically and uniformly arranging semiconductor nano-pillar polymers; the semiconductor nano-pillar polymer comprises at least two semiconductor nano-pillars which are arranged at intervals.
And the dielectric antireflection layer 3 is covered on the silicon substrate 1 and the upper surface of the semiconductor nano column polymer.
In this embodiment, the semiconductor nano-pillar is made of Si, gaAs, or Ge.
In this embodiment, the semiconductor nanorod multimer is a semiconductor nanorod dimer, a semiconductor nanorod trimer, a semiconductor nanorod tetramer, or the like.
In the embodiment, the dielectric antireflection layer 3 is made of Si 3 N 4 Or SiO 2 Or TiO 2 。
In the embodiment, the thickness of the dielectric antireflection layer 3 is 5nm to 100nm.
The preparation method of the light absorption enhancement and antireflection structure for the silicon substrate comprises the following steps:
s1, preparing a periodic array consisting of semiconductor nano-pillar polymers on a silicon substrate 1;
and S2, preparing a dielectric antireflection layer 3 on the upper surface of the silicon substrate 1 and the upper surface of the semiconductor nano column polymer.
S1, under the condition that the material of the semiconductor nano-column in the semiconductor nano-column polymer is Si, the preparation method of the semiconductor nano-column polymer is an electron beam exposure technology, a focused ion beam technology or a nanoimprint technology;
under the condition that the material of the semiconductor nano-pillar in the semiconductor nano-pillar polymer is Ge or GaAs, the preparation method of the semiconductor nano-pillar polymer comprises the following steps: firstly, preparing a semiconductor nano film on the upper surface of a silicon substrate 1 by adopting an electron beam evaporation method, and then preparing a semiconductor nano column polymer on the semiconductor nano film by adopting an electron beam exposure technology or a focused ion beam technology or a nano imprinting technology.
In S2, the preparation method of the medium antireflection layer 3 is a chemical vapor deposition method or an electron beam evaporation method.
The test method for the light absorption enhancement and antireflection structure of the silicon substrate comprises the following steps of carrying out simulation calculation by using a time domain finite difference method:
firstly, constructing a physical model of a periodic unit in a light absorption enhancement and antireflection structure for a silicon substrate; then setting a perfect matching layer on the upper and lower boundaries of the physical model, setting periodic boundary conditions on the peripheral boundaries, and setting a beam of plane waves which are vertically incident on the upper surface; and calculating the transmission spectrum and the reflection spectrum of the corresponding physical model.
Compared with the existing composite structure of the dielectric antireflection layer and the metal nanoparticle array, the structure in the embodiment can generate a plurality of mie resonances which have lower absorption loss and obvious forward scattering effect, can play an antireflection effect on the surface of the silicon substrate 1 in a wider band range and enhance the absorption of the silicon substrate 1 to incident light, and overcomes the limitation that the composite structure of the dielectric antireflection layer and the metal nanoparticle array only has better antireflection performance in a specific band and the light absorption enhancement of the silicon substrate 1 is limited by the larger absorption loss of a metal material.
The technical solutions related to the above embodiments are described below with reference to a preferred embodiment.
Example 1
As shown in FIG. 1, the light absorption enhancing and antireflection structure for the silicon substrate comprises a semiconductor nano-pillar polymer periodic array 2 and a dielectric antireflection layer 3 on the uppermost layer, wherein the semiconductor nano-pillar polymer periodic array 2 is a silicon nano-pillar dimer periodic array, and the dielectric antireflection layer 3 is Si 3 N 4 And a dielectric antireflection layer.
The light absorption enhancing and anti-reflection structure for the silicon substrate in the embodiment comprises the following preparation steps:
(1) Preparing a periodic array consisting of silicon nanorod dimers on a silicon substrate 1;
(2) Preparing a layer of Si on the basis of the step (1) 3 N 4 And a dielectric antireflection layer.
Wherein the heights of the silicon nano-column dimers are all 125nm; the diameters of two silicon nano-columns in the silicon nano-column dimer are respectively 80nm and 100nm; the gap between two silicon nano-columns in the silicon nano-column dimer is 40nm, the periodic array of the silicon nano-column dimer is a square array, and the period is 500nm; si 3 N 4 The thickness of the medium antireflection layer is 60nm.
Using the time domainThe finite difference method is used for carrying out simulation calculation, firstly, a physical model of a periodic unit of the light absorption enhancement and antireflection structure used for the silicon substrate in the embodiment is built, then, the upper boundary and the lower boundary of the physical model are set to be perfect matching layers, the peripheral boundaries are set to be periodic boundary conditions, a beam of plane wave which is vertically incident is arranged on the upper surface, and then, the transmission spectrum and the reflection spectrum of the corresponding physical model are calculated. In simulation calculations, the refractive index of silicon is derived from experimental data of Palik, air and Si 3 N 4 Are set to 1 and 2, respectively.
FIG. 3 is a graph of the reflection curves of the structure and the bare silicon structure in the present embodiment under the irradiation of the normal incident light in the 400-1100nm band, which is calculated by using the finite difference time domain method. As can be seen from fig. 3, in the wavelength range of 400-1100nm, the structure in this embodiment can achieve a better antireflection effect in the entire wavelength range, the average reflectivity is 2.6%, the average reflectivity of the bare silicon structure is about 35%, and the average reflectivity of the structure in this embodiment is far lower than the average reflectivity of the bare silicon structure.
FIG. 4 is a graph of transmission curves of the structure and the bare silicon structure in the present embodiment under the irradiation of normal incident light in the 400-1100nm band, which is calculated by using the finite difference time domain method. As can be seen from fig. 4, in the wavelength range of 400-1100nm, the structure in this embodiment can achieve a better light absorption enhancement effect in the whole wavelength range, and the average transmittance, i.e., the light/incident light entering the silicon substrate is 93%, and the average transmittance of the bare silicon is about 65%.
Comparative example 1
As shown in fig. 2, a structure of a dielectric antireflection layer 3 combined with a semiconductor nano-pillar periodic array 4 includes a semiconductor nano-pillar periodic array 4 on a silicon substrate 1 and an uppermost dielectric antireflection layer 3. The semiconductor nano-pillar periodic array 4 is a silicon nano-pillar periodic array, and the dielectric antireflection layer 3 at the uppermost layer is Si 3 N 4 And a dielectric antireflection layer.
The preparation of the structure in this comparative example comprises the following preparation steps:
(1) Preparing a periodic array consisting of silicon nano-pillars on a silicon substrate 1;
(2) Preparing a layer of Si on the basis of the step (1) 3 N 4 And a dielectric antireflection layer.
Wherein the height and the diameter of the silicon nano-column are respectively 125nm and 100nm; the silicon nano-pillar periodic array is a square array, and the period is 500nm; si 3 N 4 The thickness of the dielectric antireflection layer is 60nm.
A time domain finite difference method is used for simulation calculation, a physical model of a periodic unit in the structure of the comparative example is firstly constructed, then the upper boundary and the lower boundary of the physical model are set as perfect matching layers, the peripheral boundaries are set as periodic boundary conditions, a beam of plane wave which is vertically incident is arranged on the upper surface, and then the transmission spectrum and the reflection spectrum of the corresponding physical model are calculated. In the simulation calculations, the refractive index of silicon is derived from experimental data of Palik, air and Si 3 N 4 Are set to 1 and 2, respectively.
FIG. 5 is a graph showing the transmission spectrum and the reflection spectrum of the structure of the comparative example under the irradiation of the normally incident light of 400-1100nm band calculated by using the finite difference time domain method. As can be seen from FIG. 5, the structure can also achieve better antireflection and light absorption enhancement effects within the wavelength range of 400-1100nm, with an average transmittance of 92% and an average reflectance of 5.2%. This value is twice the average reflectivity of the structure in example 1.
Compared with the structure in which the dielectric antireflection layer 3 is combined with the semiconductor nanorod periodic array 4, the semiconductor nanorod multimeric periodic array 2 in the structure of example 1 can generate more mie resonances than the semiconductor nanorod array 4, and thus can perform antireflection effects and light absorption enhancement at wider wavelength bands.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (9)
1. A light absorption enhancement and antireflection structure for a silicon substrate,
the method comprises the following steps:
the semiconductor nano-column polymer periodic array (2) is positioned on the upper surface of the silicon substrate (1), and the semiconductor nano-column polymer periodic array (2) is formed by periodically and uniformly arranging semiconductor nano-column polymers;
and the dielectric antireflection layer (3) covers the silicon substrate (1) and the upper surface of the semiconductor nano column polymer.
2. The light absorption enhancement and antireflection structure for a silicon substrate of claim 1,
the semiconductor nano-column is made of Si or GaAs or Ge.
3. The light absorption enhancement and antireflection structure for a silicon substrate of claim 1,
the semiconductor nano-pillar polymer is a semiconductor nano-pillar dimer, a semiconductor nano-pillar trimer or a semiconductor nano-pillar tetramer.
4. The light absorption enhancement and antireflection structure for a silicon substrate of claim 1,
the medium antireflection layer (3) is made of Si 3 N 4 Or SiO 2 Or TiO 2 。
5. The light absorption enhancement and antireflection structure for a silicon substrate of claim 1,
the thickness of the medium antireflection layer (3) is 5 nm-100 nm.
6. A method for preparing a light absorption enhancing and antireflection structure for a silicon substrate is characterized in that,
the method comprises the following steps:
s1, preparing a periodic array consisting of semiconductor nano-column polymers on a silicon substrate (1);
s2, preparing a dielectric antireflection layer (3) on the upper surface of the silicon substrate (1) and the upper surface of the semiconductor nano column polymer.
7. The method of claim 6, wherein the light absorption enhancement and antireflection structure for the silicon substrate,
in S1, under the condition that the material of the semiconductor nano-column in the semiconductor nano-column polymer is Si, the preparation method of the semiconductor nano-column polymer is an electron beam exposure technology, a focused ion beam technology or a nanoimprint technology;
under the condition that the material of the semiconductor nano-pillar in the semiconductor nano-pillar polymer is Ge or GaAs, the preparation method of the semiconductor nano-pillar polymer comprises the following steps: firstly, preparing a semiconductor nano film on the upper surface of a silicon substrate (1) by adopting an electron beam evaporation method, and then preparing a semiconductor nano column polymer on the semiconductor nano film by using an electron beam exposure technology or a focused ion beam technology or a nano imprinting technology.
8. The method of claim 6, wherein the light absorption enhancement and antireflection structure for the silicon substrate,
in S2, the preparation method of the dielectric antireflection layer (3) is a chemical vapor deposition method or an electron beam evaporation method.
9. A method for testing a light absorption enhancement and antireflection structure of a silicon substrate is characterized in that,
the method comprises the following steps of performing simulation calculation by using a time domain finite difference method:
firstly constructing a physical model of a periodic unit in a light absorption enhancement and antireflection structure for a silicon substrate, which is described in any one of claims 1 to 5 or prepared by the method described in any one of claims 6 to 8;
then setting the upper and lower boundaries of the physical model as perfect matching layers, setting the peripheral boundaries as periodic boundary conditions, and setting a beam of plane waves which are vertically incident on the upper surface;
and calculating the transmission spectrum and the reflection spectrum of the corresponding physical model.
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