CN110648728A - Method for predicting passivation effect of organic molecules on silicon surface - Google Patents
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Abstract
The invention provides a method for predicting the passivation effect of organic molecules on a silicon surface, which adopts a first principle method based on a density functional to predict and comprises the following steps: establishing an adsorption model of organic molecules and the silicon surface, calculating adsorption energy, and determining a stable passivation structure when the organic molecules passivate the silicon surface; calculating the electronic structure attribute, the charge transfer condition and the bonding condition of the stable passivation structure interface; and judging the passivation ratio of silicon surface atoms and the passivation strength of the silicon surface atoms, and predicting the passivation effect. The prediction method can quickly judge the passivation structure, can also be used for searching and designing a proper organic passivation material to guide the synthesis of an experiment, saves time and cost, reduces the interference of human factors and environmental factors in the experiment process, and has high reliability and good reproducibility.
Description
Technical Field
The invention relates to material passivation, in particular to a method for predicting the passivation effect of organic molecules on silicon surfaces.
Background
Solar energy is the source of all energy sources of the earth, and how to better apply the clean green renewable energy source, namely the solar energy, is a topic concerned by the national and scientific workers today when other non-renewable energy sources of the earth are exhausted. The process of converting solar energy into electrical energy is called solar photovoltaic power generation, and the core tool for realizing the process is a solar cell. In 1883 the first solar cell was successfully made by Charles frits, which formed a semiconductor metal junction on a selenium semiconductor with a very thin gold layer, but the device had only 1% efficiency.
With the development of technology, solar cells made of various materials have been developed, wherein the silicon solar cells have appropriate forbidden band width, no environmental pollution, convenience for industrial production, and high photoelectric conversion efficiency, and are favored by people, and are dominant among solar cells made of various materials. Theoretically, the maximum conversion efficiency of a silicon solar cell is 29%, and most of energy loss in energy sources of incident light is from transmission loss and quantum loss, and about 10% is carrier recombination, surface reflection loss, series resistance loss, and the like. However, defects and impurities existing on the silicon surface greatly affect the performance of devices, and in order to reduce the cost and improve the conversion efficiency of solar cells, various silicon surface passivation technologies are developed, and surface electrons can be neutralized through surface passivation, so that the defects and electron recombination centers caused by the surfaces are reduced, the silicon surface passivation technology is very important for prolonging the service life of carriers of crystalline silicon, and plays a key role in the aspect of solar cells. The existing passivation method mainly comprises chemical passivation, field effect passivation, electrochemical passivation and the like.
The chemical passivation adopts a method that atoms in a passivation material and atoms on the surface of crystalline silicon form chemical bonds, so that the purpose of inhibiting surface recombination is achieved, and dangling bonds are radically eliminated. Most typical materials for chemical passivationIs SiO2And hydrogenated amorphous silicon (a-Si: H). SiO 22Filling silicon surface dangling bonds with Si-O bonds, but SiO2In order to overcome the difficulty that the passivation technology needs a high temperature of 900 ℃, a wet oxidation technology is developed, such as a back contact tunnel oxide passivation contact (TopCon) cell developed by Fraunhofer ISE institute of solar energy, and the conversion efficiency reaches 25%. H-Si thin film passivation utilizes H-Si-Si and Si-H bonds to fill Si dangling bonds, but PECVD equipment adopted by the method is expensive, and the process for producing the ultrathin amorphous silicon thin film is difficult to control.
The field effect passivation is to introduce a passivation material (such as SiNx, Al) with fixed charges therein2O3) The coulomb electrostatic field of the charge repels the carriers and retards the combination of the carriers and the surface defects, thereby realizing the aim of inhibiting the surface recombination. The SiNx film is a passivation anti-reflection film which is most commonly used in the production of crystalline silicon solar cells, has fixed positive charges, has a good passivation effect on n-type silicon surfaces, and has a poor passivation effect on highly doped p + surfaces. Another typical application of the field effect passivation mechanism is Al2O3And (5) passivating the film. In contrast to SiNx films, Al2O3The contact surface of the film and the silicon has high fixed negative charge and can shield electrons on the surface of the p-type silicon, so that Al2O3The film has a good field passivation effect on the surface of the p-type silicon, and is mainly applied to the back passivation of the p-type cell at present. The PERC battery is formed by adding Al on the basis of the traditional p-type battery2O3Back passivation, conversion efficiency is obviously improved.
In addition to chemical passivation and field effect passivation, the electrochemical passivation mechanism has applications and studies. Electrochemical passivation is still chemical passivation in nature, and its principle is to use the atoms in electrolyte to combine with silicon surface atoms, and it is characterized by that the combination can be controlled by charge transfer.
Although conventional passivation techniques such as silicon oxide, aluminum oxide and amorphous silicon thin films are well established, their preparation usually requires severe conditions such as high temperature processes or high vacuum equipment, which severely hinders the cost reduction of devices. The organic molecule is adopted to passivate the silicon surface, so that the method has the advantages of low cost and mild reaction conditions. The passivation effect of the organic small-molecule TFSI on the surface of a C-Si device is proved, and the super acid can generate millisecond-order minority carrier lifetime when being used for passivating a silicon wafer. However, screening among the many possible passivation materials is required, and it takes a lot of time to perform the test before a small number of satisfactory test results are possible.
In summary, on the basis of the prior art, it is one of the technical problems to be solved at present to deeply and carefully study the passivation mechanism and the passivation nature of the organic molecules on the silicon wafer and predict the passivation effect of the organic molecules on the surface of the silicon wafer.
Disclosure of Invention
The invention aims to provide a method for predicting the passivation effect of organic molecules on silicon surfaces.
The purpose of the invention is realized as follows:
a method for predicting the passivation effect of organic molecules on silicon surface by adopting a first principle method based on density functional comprises the following steps:
(a) establishing an adsorption model of organic molecules and the silicon surface, calculating adsorption energy, and determining a stable passivation structure when the organic molecules passivate the silicon surface;
(b) calculating the electronic structure attribute, the charge transfer condition and the bonding condition of the stable passivation structure interface;
(c) and (c) judging the passivation proportion of silicon surface atoms according to the result of the step (a), judging the passivation strength of the silicon surface atoms according to the result of the step (b), and predicting the passivation effect.
In step (a), the adsorption energy EadsIs defined as the difference between the total energy after adsorption and the energy of the organic molecules and the pure silicon surface, the number of bonding silicon atoms is averaged and expressed by a formula as follows:
Eads=(Etotal – Eorganic molecules -E’)/n
Wherein E istotalFor organic molecules adsorbed on a pure semiconductorTotal energy of the surface of the bulk material, EOrganic moleculesAnd E' respectively represent the energy of the organic molecules and the energy of the pure silicon surface, and n is the number of atoms on the passivated silicon surface.
In step (a), the stable passivation structure is determined by comparing the adsorption energies of various structures, and the lower the adsorption energy, the more stable the structure, according to the energy minimization principle.
Specifically, the organic molecule is bis (trifluoromethyl) sulfonimide (TFSI), and the silicon surface is a Si (001) surface.
In the step (b), Bader charges and ELFs (electronic local area functions) of the stable passivation structure (the model with the lowest energy) are calculated by adopting first-nature principle software respectively, the Bader charges are adopted to judge the charge transfer condition of silicon surface atoms, and the ELFs are adopted to judge the bonding strength of the silicon surface atoms and organic molecules.
In the step (c), analyzing the result of the step (a), namely the passivation structure of the organic molecules on the silicon surface, and calculating the ratio of the number of the bonding of the silicon surface atoms and the organic molecules to the number of the non-bonding as the basis for judging the passivation effect of the silicon surface, wherein the more the number of the bonding is, the more the passivation effect is obvious.
And (c) obtaining the electronic structure attribute after the silicon surface organic molecule passivation according to the result of the step (b), analyzing the electronic structure attribute to obtain the gain and loss condition of the silicon surface charge, and taking the gain and loss condition as another basis for judging the silicon surface passivation effect, wherein the stronger the bonding, the more the charge transfer and the higher the passivation degree.
The invention uses a first principle method to establish an adsorption model of organic molecules on the silicon surface, and researches a microscopic mechanism of organic molecules for passivating the silicon material surface by calculating adsorption energy, Bader charge, ELF (electronic local area function) and the like of the organic molecules on the silicon material surface, thereby predicting the passivation effect. The theoretical prediction method can be used for predicting the passivation effect of the existing material on the silicon surface, effectively avoids the blindness of the experiment and the waste of a large amount of resources, quickly judges the passivation structure, guides the synthesis of the experiment, and saves time and cost; the method can also be used for searching and designing a proper organic passivation material, searching or efficiently designing a passivation material with a good passivation effect on the basis of a predicted result, and improving the scientific research efficiency. The prediction method reduces the interference of human factors and environmental factors in the experimental process, and has high reliability and good reproducibility.
Drawings
FIG. 1 is a schematic diagram of the prediction process of the effect of passivating Si surface by TFSI molecules.
FIG. 2 is a TFSI-Structural models of ionic groups.
FIG. 3 shows a structural unit of the Si (001) plane.
FIG. 4 is a TFSI-Adsorption model in which the ionic group adsorbs Si (001) in the OA direction.
FIG. 5 is a TFSI-Adsorption mode in which ionic groups adsorb Si (001) in the OB direction.
FIG. 6 is a TFSI-The Bader charges before and after the group is bonded with the Si surface layer are lost, the plus represents the electron, and the minus represents the electron loss.
FIGS. 7 (a) and (b) are TFSI, respectively-ELF graphs of the left and right sides after the group is bonded with the Si surface layer.
Detailed Description
The invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention in any way.
Procedures and methods not described in detail in the following examples are conventional methods well known in the art, and the reagents used in the examples are either analytically or chemically pure and are either commercially available or prepared by methods well known to those of ordinary skill in the art. The following examples all achieve the objects of the present invention.
The computing tool used by the invention is a VASP software package based on a Density Functional Theory (DFT) framework, and the pseudopotential adopts potpaw-PBE, namely GGA-PBE. The convergence criterion of the self-consistent field is set to EDIFF =1 × 10 with the plane wave cut-off energy set to 500eV-6Within eV/atom. In the calculation, a (001) surface of Si is selected for adsorption, and a special k-point method in a Monkhrst-Pack form is adopted for Brillouin zone integration. The Si (001) -faced substrate has a slight structural feature when it is extended in both directions A, BThe difference is as follows: the dangling bonds on the surface of the Si in the direction A are arranged in parallel and have equal distance; the hanging keys in the B direction are parallel pairwise, and the distance between each pair of hanging keys and the adjacent hanging key is slightly longer than that in the A direction. The special k-point of the Monkhrst-Pack network of the A-direction extending structure is taken as 2X 4X 1, and the k-point of the B-direction extending structure is taken as 4X 2X 1.
In the embodiment of the invention, organic micromolecules TFSI and Si are adopted as adsorbing materials, wherein the Si (001) surface is an adsorbing surface, the passivation effect of the organic micromolecules TFSI on the silicon surface is researched, and the flow schematic diagram of the prediction method is shown in figure 1.
Firstly, calculating an adsorption structure of the surface of the organic molecule passivated silicon, calculating adsorption energy, and determining an adsorption mode and an adsorption structure; and then, calculating the electronic structure attribute, the charge transfer condition and the bonding condition of an interface when the organic molecules passivate the silicon surface, finally, judging the passivation proportion of silicon surface atoms according to the adsorption structure, judging the passivation strength of the silicon surface atoms according to the electronic structure attribute, and predicting the passivation effect.
Firstly, establishing an adsorption model of a TFSI molecule passivation Si (001) surface, calculating adsorption energy of the TFSI molecule passivation Si (001) surface, and determining a stable passivation structure when the TFSI molecule passivation Si (001) surface.
TFSI (trifluromethyl sulfonimide), Chinese name bis (trifluoromethyl) sulfonimide, molecular formula C2HF6NO4S2Molecular weight 281.15; at normal temperature, the bis (trifluoromethyl) sulfimide is colorless needle-shaped crystal; TFSI is easy to absorb water, is easy to dissolve in water, alcohols and ethers, is insoluble in n-hexane, benzene and the like, can be fuming when exposed to air, is easy to sublimate, and has strong acidity and certain toxicity.
Because TFSI molecules are strong acid, H is easily ionized in solution+Forming TFSI-Ionic groups, therefore the adsorption model employs the ionic form of TFSI "TFSI-The structural schematic of the ionic group is shown in FIG. 2. A schematic diagram of the structural unit of the Si (001) plane is shown in FIG. 3. TFSI is realized by different distribution characteristics of dangling bonds on the surface of Si in different directions-The passivation of the ionic groups on the Si surface has two directions of OA and OB, i.e.There are two possible structures F1, F2, whose schematic diagrams are shown in fig. 4 and 5, respectively. The results of the calculations based on the established adsorption model are summarized in table 1.
TABLE 1 adsorption energy of TFSI for adsorption of Si
Remarking: the adsorption energy can be represented by the formulaE ads=(E total– E Organic molecules -E’) Calculated as
Analysis of the results in Table 1 shows that the adsorption energy of TFSI molecules adsorbed on the surface of Si is negative, which means that TFSI can achieve passivation effect on Si by adsorption. In both adsorption models, the lowest energy of F1 is most stable under this configuration.
Next, the corresponding model of F1 (fig. 4) was further calculated, and its Bader charge (fig. 6) and ELF (electron local function) were calculated, respectively (fig. 7). From the Bader charge transfer case point of view, the charge is transferred from the Si atom to the O atom and the S atom, thereby weakening the ability to combine with carriers. From the character of atom bonding before and after reaction, before reaction, the O atom and S atom in TFSI molecule form covalent bond with stronger local property; after the reaction, the bonding locality at the corresponding position is weakened, and the strength of the formed covalent bond is weakened. The local nature of the bonds of the Si atoms to the O atoms is centered, but the change in the local distribution characteristics of the electrons may demonstrate that the binding of the TFSI molecules to Si results in a reduction in the surface activity of Si.
Finally, the above calculation results, TFSI, are combined-The passivation effect of the group on the Si (001) plane is derived from the combination of O atoms and Si atoms, and neutralizes dangling bonds that are likely to become recombination centers on the Si surface. In the model, the number of silicon surface atoms bonded to organic molecules was 4, the number of non-bonded atoms was 0, and the passivation ratio was 100%. From the electron gain and loss conditions before and after passivation, the process of transferring charges from Si atoms to O atoms is a bonding process, the Si atoms with four bonds have a larger number of charges transferred, the activity of Si is weakened, and the passivation effect is achieved。
Claims (6)
1. A method for predicting the passivation effect of organic molecules on silicon surface is characterized in that a first principle method based on density functional is adopted for prediction, and the method comprises the following steps:
(a) establishing an adsorption model of organic molecules and the silicon surface, calculating adsorption energy, and determining a stable passivation structure when the organic molecules passivate the silicon surface;
(b) calculating the electronic structure attribute, the charge transfer condition and the bonding condition of the stable passivation structure interface;
(c) judging the passivation proportion of silicon surface atoms according to the result of the step (a), judging the passivation strength of the silicon surface atoms according to the result of the step (b), and then predicting the passivation effect.
2. The method for predicting the passivation effect of organic molecules on silicon surface according to claim 1, wherein in the step (a), the adsorption energy EadsThe difference between the total energy after adsorption and the energy of organic molecules and pure silicon surface is obtained by averaging the number of bonding silicon atoms, and the number is expressed by a formula as follows: eads=(Etotal – EOrganic molecules-E')/n, wherein EtotalTotal energy, E, of organic molecules adsorbed on the surface of a pure semiconductor materialOrganic moleculesAnd E' respectively represent the energy of the organic molecules and the energy of the pure silicon surface, and n is the number of atoms on the passivated silicon surface.
3. The method according to claim 1, wherein the stable passivation structure is determined by comparing the adsorption energies of the passivation structures in step (a), and the lower the adsorption energy, the more stable the structure.
4. The method according to claim 1, wherein in step (b), Bader charges and electron local functions of the stable passivation structure are calculated by first principle software, Bader charges are used to determine charge transfer of silicon surface atoms, and electron local functions are used to determine bonding strength between silicon surface atoms and organic molecules.
5. The method according to claim 1, wherein in the step (c), the result of the step (a) is analyzed, and the ratio of the number of bonds formed between silicon surface atoms and organic molecules to the number of non-bonds is calculated as a basis for judging the passivation effect of the silicon surface, wherein the passivation effect is more obvious as the number of bonds is larger.
6. The method according to claim 1, wherein in step (c), the electronic structure property of the passivated organic molecules on the silicon surface is obtained according to the result of step (b), the gain and loss of the silicon surface charge is obtained by analyzing the electronic structure property, and the stronger the bonding, the more the charge transfer and the higher the passivation degree.
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