CN107747122B - Method for optimizing solid-liquid interface oxygen distribution regulation in Czochralski silicon single crystal growth process - Google Patents

Method for optimizing solid-liquid interface oxygen distribution regulation in Czochralski silicon single crystal growth process Download PDF

Info

Publication number
CN107747122B
CN107747122B CN201710811360.3A CN201710811360A CN107747122B CN 107747122 B CN107747122 B CN 107747122B CN 201710811360 A CN201710811360 A CN 201710811360A CN 107747122 B CN107747122 B CN 107747122B
Authority
CN
China
Prior art keywords
solid
oxygen concentration
liquid interface
crystal
melt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710811360.3A
Other languages
Chinese (zh)
Other versions
CN107747122A (en
Inventor
刘丁
任俊超
张新雨
张晶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xi'an Xinhui Equipment Technology Co ltd
Xian Eswin Material Technology Co Ltd
Original Assignee
Xian University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian University of Technology filed Critical Xian University of Technology
Priority to CN201710811360.3A priority Critical patent/CN107747122B/en
Publication of CN107747122A publication Critical patent/CN107747122A/en
Application granted granted Critical
Publication of CN107747122B publication Critical patent/CN107747122B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/20—Controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B30/00—Production of single crystals or homogeneous polycrystalline material with defined structure characterised by the action of electric or magnetic fields, wave energy or other specific physical conditions
    • C30B30/04—Production of single crystals or homogeneous polycrystalline material with defined structure characterised by the action of electric or magnetic fields, wave energy or other specific physical conditions using magnetic fields

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

本发明公开了一种直拉硅单晶生长工艺优化固液界面氧分布调节方法，首先调节超导水平磁场强度，得到不同磁场强度下的固液界面氧浓度分布曲线，计算固液界面的平均氧浓度和固液界面径向氧浓度分布的均匀性，通过对比选取出合适的磁场强度，其次是在选取的磁场强度下分别调节晶体转速和坩埚转速，通过对比仿真结果得到适合降低固液界面氧浓度和提高固液界面氧浓度分布均匀性的晶体转速和坩埚转速，最后在所选取的超导磁场强度、晶体转速和坩埚转速三者的共同作用下，得到超导水平磁场下直拉硅单晶固液界面氧浓度分布信息，本发明解决了现有技术中存在的直拉硅单晶生长工艺参数调节时容易造成晶体中氧含量过高、氧分布不均匀的问题。

Figure 201710811360

The invention discloses a method for adjusting the oxygen distribution at the solid-liquid interface for optimizing a Czochralski silicon single crystal growth process. First, the superconducting horizontal magnetic field intensity is adjusted to obtain the oxygen concentration distribution curve of the solid-liquid interface under different magnetic field intensities, and the average value of the solid-liquid interface is calculated. The uniformity of the oxygen concentration and the radial oxygen concentration distribution of the solid-liquid interface, the appropriate magnetic field strength is selected by comparison, and the second is to adjust the crystal rotation speed and the crucible rotation speed under the selected magnetic field strength. Oxygen concentration and crystal rotation speed and crucible rotation speed that improve the uniformity of oxygen concentration distribution at the solid-liquid interface. Finally, under the combined action of the selected superconducting magnetic field strength, crystal rotation speed and crucible rotation speed, Czochralski silicon under superconducting horizontal magnetic field is obtained. The information on the oxygen concentration distribution at the solid-liquid interface of the single crystal, the present invention solves the problems existing in the prior art that when the parameters of the Czochralski silicon single crystal growth process are adjusted, the oxygen content in the crystal is too high and the oxygen distribution is uneven.

Figure 201710811360

Description

Method for optimizing solid-liquid interface oxygen distribution regulation in Czochralski silicon single crystal growth process
Technical Field
The invention belongs to the technical field of adjusting methods of a magnetically controlled Czochralski silicon single crystal solid-liquid interface oxygen distribution growth process, and particularly relates to an adjusting method for optimizing the solid-liquid interface oxygen distribution of the Czochralski silicon single crystal growth process.
Background
The Czochralski method is the main method for preparing silicon single crystal semiconductor materials in the fields of integrated circuits and photovoltaic power generation. The main quality evaluation indexes of silicon single crystals in the semiconductor industry include reduction of various harmful impurity contents (oxygen, carbon) in the wafer and reduction of micro-defects, wherein secondary defects caused by the oxygen impurity content can seriously affect the quality of drawn silicon semiconductor materials and the performance of produced devices. In order to reduce the micro-defects of the crystal as much as possible and ensure the uniformity of the resistivity of the crystal, how to reduce the content of oxygen impurities in a solid-liquid interface (a crystal and melt interface) in the growth process of the large-size crystal and improve the uniformity of oxygen distribution in the solid-liquid interface has important significance.
Because the molten silicon is in a high-temperature and sealed furnace body, the oxygen distribution condition in the crucible melt and the solid-liquid interface cannot be directly obtained. At present, methods for obtaining oxygen distribution in crystals mainly include an infrared absorption method and a numerical simulation method. The infrared absorption method is to analyze the infrared spectrum by measuring the silicon wafer, and quantitatively analyze and calculate the oxygen content and the oxygen distribution uniformity on the silicon wafer according to the peak position and the absorption intensity. The numerical simulation method is characterized in that a single crystal furnace thermal field is modeled by commercial CFD software, and the distribution condition of oxygen content in a melt and in a solid-liquid interface is obtained by solving by adopting a Finite Volume Method (FVM), so that the experiment cost is low, the period is short, and the crystal growth problem can be known better and faster. The existing process adjusting method of high crystal rotating speed and low crystal rotating speed under the conventional horizontal magnetic field in the numerical simulation method easily causes the oxygen content in the crystal to be increased, and the working performance of the manufactured electronic device is seriously influenced. Therefore, the important problem to be solved at present is to provide a method for adjusting the oxygen distribution of the solid-liquid interface in the Czochralski silicon single crystal growth process, so as to reduce the oxygen concentration of the solid-liquid interface and improve the uniformity of the oxygen distribution of the solid-liquid interface in the Czochralski silicon single crystal growth process, and to meet the market demand for high-quality silicon single crystals.
Disclosure of Invention
The invention aims to provide a method for adjusting oxygen distribution of a solid-liquid interface optimized by a czochralski silicon single crystal growth process, which solves the problems that the oxygen content in the crystal is too high and the oxygen distribution is not uniform easily caused when the parameters of the czochralski silicon single crystal growth process are adjusted in the prior art.
The technical scheme adopted by the invention is that the method for optimizing the oxygen distribution adjustment of the solid-liquid interface in the czochralski silicon single crystal growth process is implemented according to the following steps:
step 1, constructing a three-dimensional local physical model required by the growth of silicon single crystal by a Czochralski method;
step 2, importing the three-dimensional local physical model into a CFX fluid simulation module, setting simulation as steady-state simulation, and setting physical parameters and superconducting magnetic field strength of silicon melt, silicon crystal, graphite crucible and quartz crucible;
step 3, solving the radial oxygen concentration distribution condition of the solid-liquid interface under different superconducting horizontal magnetic field strengths;
step 4, analyzing the influence of the crystal rotation speed on the solid-liquid interface shape and the radial temperature distribution in the melt;
step 5, analyzing the influence of the crucible rotation speed on the shape of a solid-liquid interface and the radial temperature distribution in the melt;
and 6, integrating the steps 3-5, and obtaining oxygen concentration distribution information of the solid-liquid interface of the czochralski silicon single crystal under the superconducting horizontal magnetic field under the combined action of the selected superconducting horizontal magnetic field intensity, the crystal rotating speed and the crucible rotating speed.
The present invention is also characterized in that,
the step 1 is implemented according to the following steps:
step 1.1, generating a three-dimensional local physical model for the growth of the silicon single crystal by the Czochralski method by using a Gambit software grid, wherein the three-dimensional local physical model comprises a crystal, a melt, a quartz crucible and a graphite crucible;
step 1.2, setting the radius of a quartz crucible to be 0.306m, the radius of a graphite crucible to be 0.32m, the radius of a melt in the crucible to be 0.3m, rotating the crucible anticlockwise, and setting the rotating speed of the crucible to be omegac(ii) a The radius range of the crystal is 0.15 m-0.225 m, the crystal rotates clockwise, and the rotation speed of the crystal is omegasThe height of the melt is 0.08-0.22 m, the length of the crystal is 0-0.6 m, the feeding amount is 160kg, the free interface is the interface between the silicon melt and the gas, and the solid-liquid interface is the phase interface between the crystal and the melt. Step 1.2 crucible rotation speed omegac0-10 rpm, crystal rotation speed omegasIs 0 to 16 rpm.
The step 2 is implemented according to the following steps:
step 2.1, setting the crucible to rotate anticlockwise, wherein the rotating speed of the crucible is omegacThe crystal rotates clockwise at omegas；
Step 2.2, assuming that the silicon melt is incompressible Newtonian fluid; assuming that the silicon melt satisfies the Boussinesq approximation; setting a solid-liquid interface as a flat surface, wherein a supercooled state does not occur during crystallization of the solid-liquid interface, and the temperature of the solid-liquid interface is 1685K of the melting point of silicon; setting the interface of the melt and argon, namely the free liquid level is a flat surface, the height of the free liquid level is the same as that of the solid-liquid interface, and radiating heat to the external atmosphere environment; the bottom of the quartz crucible, the inner wall of the crucible and the silicon melt meet the condition of no sliding boundary; oxygen transport processes within the melt have negligible effect on melt flow and heat transfer.
In step 2.2, the boundary conditions used in the simulation iterative solution process include an oxygen concentration boundary condition and a temperature boundary condition, wherein the oxygen concentration boundary condition is as follows:
(1) the boundary condition of the oxygen concentration at the boundary of the silicon melt and the inner wall of the quartz crucible is as follows:
Figure BDA0001403971240000031
Figure BDA0001403971240000032
Figure BDA0001403971240000041
wherein N isAIs the alpha-Galois constant of the analog-to-digital converter,
Figure BDA0001403971240000042
is the partial pressure of oxygen, aoIs the volume fraction of oxygen, R is the oxygen gas molar constant, T is the chemical reaction temperature,
Figure BDA0001403971240000043
is a chemical reaction
Figure BDA0001403971240000044
Amount of change in free energy.
(2) Oxygen concentration boundary condition at interface of silicon melt and argon gas:
Figure BDA0001403971240000045
in the formula, COAnd CsurfThe oxygen concentration in the melt and the oxygen concentration at the free liquid level, respectively; cSiIs the silicon melt concentration; dOAnd DSiOThe diffusion coefficient of oxygen in the silicon melt and the diffusion coefficient of SiO gas in the silicon meltDiffusion coefficient in argon; Δ G is the chemical reaction formula (Si)melt+Omelt＝SiOgas) Amount of change in free energy of p0Is the vapor pressure of SiO gas, R is the gas molar constant, T is the chemical reaction temperature; deltagIs the free liquid level boundary layer thickness;
in the actual growth environment of the crystal, the oxygen concentration C of the free liquid surface is blown by argon gassurfOnly the internal oxygen concentration C of the meltOTen thousand of (a), thus the oxygen concentration C of the free liquid surfacesurfNeglecting, the oxygen concentration boundary condition of the free liquid surface is simplified to
CO＝0mol/m3；
(3) Oxygen concentration boundary conditions at solid-liquid interface (crystal growth interface):
Figure BDA0001403971240000046
wherein D is the diffusion coefficient of oxygen, VgThe moving speed of the solid-liquid interface, k is the segregation coefficient of oxygen, CoIs the oxygen concentration in the melt. Experiments show that the segregation coefficient of oxygen is close to unit 1, and more than 99 percent of oxygen is volatilized into argon from a free liquid surface, so that the content of oxygen doped into crystals is ignored in the whole oxygen flux balance of a solid-liquid interface, and the formula is simplified into that
Figure BDA0001403971240000047
In the temperature boundary condition, the bottom of the graphite crucible and the outer wall of the graphite crucible are applied with equal gradient temperature distribution values, and a heat flux density equation is established at the free liquid level, which is as follows:
Figure BDA0001403971240000051
Ql'＝qout,k-qin,k＝σεT4-εqin,k
qin,k＝sumj＝1～N(Fk,jqout,j)
wherein β [ T (r) -T0(r)]1.25Describing the heat loss due to gas convection, Ql' to describe the heat loss of the melt level by radiation, T is the free level temperature, T0Is ambient temperature, KlFor the heat transfer coefficient of the silicon melt, β is the heat loss coefficient of gas convection, r is the free liquid surface radius, ε is the emissivity, σ is the Stefan-Boltzmann constant, Fk,jIs the angular coefficient between the two surfaces of k, j, qout,kIs the heat flow out of the surface, qin,kThe heat flow flowing into the surface is shown, x and z are direction variables of a space rectangular coordinate system, and N is the total number of the surface;
similar heat flux density equations are also established at the top surfaces of the graphite crucible and the quartz crucible, the inner surface of the quartz crucible not in contact with the silicon melt, and the solid surfaces such as the outer surface of the crystal, as follows:
Figure BDA0001403971240000052
Qs'＝qout,k-qin,k＝σεT4-εqin,k
wherein Q iss' to describe the heat loss from a solid surface by radiation, KsThe thermal conductivity of the silicon melt is shown as r, the radius of the crystal or the inner radius of the quartz crucible is shown as r, and y is a direction variable of a space rectangular coordinate system.
In the iterative solution control, the number of iterations is set to 90000, the time factor is set to 1, and the residual value of the convergence curve is set to 1E-06.
Step 3 is specifically implemented according to the following steps:
step 3.1, using a numerical solver of the CFX module to numerically solve the crystal rotation speed omega under different superconducting horizontal magnetic field strengthssAnd the rotational speed omega of the cruciblecBoth flow and heat transfer within the crucible melt at 0 rpm;
step 3.2, obtaining a temperature distribution cloud picture and oxygen concentration of the melt through post-processing of the CFX module after iteration convergenceAnd tracking the position of a isotherm of the solid-liquid interface 1685K on the temperature distribution cloud chart to obtain oxygen concentration distribution data on the solid-liquid interface and obtain a relation curve of the oxygen concentration and the crystal diameter, namely a radial oxygen concentration distribution curve of the solid-liquid interface. According to the average oxygen concentration at solid-liquid interface
Figure BDA0001403971240000061
Mean square error MSE of radial oxygen concentration profileOSum gradient error sum deltaOAnd selecting proper superconducting magnetic field intensity as a minimum principle. Wherein the average oxygen concentration
Figure BDA0001403971240000062
Used for measuring the oxygen concentration of the solid-liquid interface, and the mean square error MSEOSum gradient error sum deltaOUsed for measuring the uniformity of oxygen concentration distribution at solid-liquid interface, as shown in the following formula
Figure BDA0001403971240000063
Wherein n is the number of collected oxygen data on the solid-liquid interface, ciIs an oxygen data point, i is an oxygen data independent variable;
Figure BDA0001403971240000064
Figure BDA0001403971240000065
wherein, gradOiIs the gradient, gradO, of each oxygen data point on the solid-liquid interface radial oxygen concentration distribution curveminIs the minimum gradient, gradient error sum delta of the radial oxygen concentration distribution curve of the solid-liquid interfaceOThe smaller the average particle diameter, the more uniform the radial oxygen concentration distribution at the solid-liquid interface.
Step 4 is specifically implemented according to the following steps:
step 4.1, in the CFX pretreatment setting, setting the appropriate magnetic field intensity selected in the step 3, and rotating the crucible at the rotating speedωcSet to 0rpm, adjust different crystal rotation speeds omegasIteratively solving until a residual error curve converges, thereby obtaining oxygen concentration data on a solid-liquid interface 1685K isotherm;
step 4.2, obtaining a relation curve between the oxygen concentration and the crystal diameter, namely a radial oxygen concentration distribution curve of the solid-liquid interface, in order to analyze the influence of the crystal rotation speed on the shape of the solid-liquid interface and the radial temperature distribution in the melt, wherein the temperature detection position is taken from the inside of the melt, is 0.08m away from the interface of the melt and argon, has the length of 0.3m, points to a crystal growth axis from the interface of the crucible and the melt in the direction, and points to the crystal growth axis according to the average oxygen concentration of the solid-
Figure BDA0001403971240000071
Mean square error MSE of radial oxygen concentration profileOSum gradient error sum deltaOFor the minimum principle, the proper crystal rotation speed is selected.
Step 5 is specifically implemented according to the following steps:
step 5.1, in the CFX pretreatment setting, setting the magnetic field intensity to be the proper magnetic field intensity selected in the step 3, and setting the crystal rotation speed omegasIs 0rpm, the rotating speed omega of the crucible is adjustedcIteratively solving through a numerical solver until a residual error curve converges, thereby obtaining oxygen concentration data on a solid-liquid interface 1685K isotherm;
step 5.2, obtaining a relation curve between the oxygen concentration and the crystal diameter, namely a solid-liquid interface radial oxygen concentration distribution curve, in order to analyze the influence of the crucible rotation speed on the solid-liquid interface shape and the melt internal radial temperature distribution, wherein the temperature detection position is taken from the inside of the melt, the height is 0.08m away from the melt-argon interface, the length is 0.3m, the direction is from the crucible to the melt interface to the crystal growth axis, and the average oxygen concentration of the solid-liquid interface is based on
Figure BDA0001403971240000072
Mean square error MSE of radial oxygen concentration profileOSum gradient error sum deltaOFor the minimum principle, the proper crystal rotation speed is selected.
Step 6 is implemented according to the following steps:
step 6.1, in the CFX pretreatment setting, setting the superconducting horizontal magnetic field intensity and the crucible rotating speed as the proper superconducting horizontal magnetic field intensity and the crucible rotating speed selected in the step 3 and the step 5, and because the high crystal rotation is favorable for improving the consistency of a solid-liquid interface, firstly, the crystal rotating speed omega is setsSetting the crystal transition as high crystal transition, and obtaining a solid-liquid interface radial oxygen concentration distribution curve through numerical iteration solution and MATLAB mapping;
step 6.2, rotating the crystal at the speed omegasSetting the crystal transition as low crystal transition, and obtaining a solid-liquid interface radial oxygen concentration distribution curve through numerical iteration solution and MATLAB mapping;
step 6.3, calculating the crystal rotation speed omega respectivelysThe average oxygen concentration of the solid-liquid interface in the radial oxygen concentration distribution curve of the solid-liquid interface at the time of high crystal transition and low crystal transition
Figure BDA0001403971240000073
And mean square error MSE associated with uniformity of oxygen concentration distributionOSum gradient error sum deltaOThrough quantitative and qualitative comparative analysis, the superconducting horizontal magnetic field intensity, the crystal rotating speed and the crucible rotating speed which are suitable for reducing the oxygen concentration of the solid-liquid interface and improving the radial oxygen concentration distribution uniformity of the solid-liquid interface are obtained through selection.
The method for adjusting the oxygen distribution of the solid-liquid interface optimized by the czochralski silicon single crystal growth process has the advantages that the oxygen concentration distribution state in the crucible melt and the oxygen concentration distribution information of the solid-liquid interface can be intuitively and accurately recognized by establishing a three-dimensional numerical value to simulate the czochralski silicon single crystal growth process, and the oxygen content and the oxygen impurity distribution uniformity in the crystal can be qualitatively analyzed according to the oxygen concentration distribution curve of the solid-liquid interface. And on the basis of quantitative analysis, the arithmetic mean value of oxygen concentration data is used for measuring the oxygen concentration of the solid-liquid interface, the mean square error of the oxygen concentration data and the gradient error of an oxygen concentration distribution curve are used for measuring the uniformity of the oxygen concentration distribution of the solid-liquid interface. The combination of qualitative analysis and quantitative analysis results shows that the process adjusting method of low crystal rotation speed and low crucible rotation speed under the selected proper magnetic field strength can effectively reduce the oxygen concentration of the solid-liquid interface and improve the radial oxygen concentration distribution uniformity of the solid-liquid interface, thereby achieving the purposes of reducing the content of oxygen impurities in the silicon crystal and improving the oxygen distribution uniformity in the crystal, and further improving the quality of the large-size silicon single crystal.
Drawings
FIG. 1 is a three-dimensional numerical simulation silicon single crystal growth schematic diagram of a solid-liquid interface oxygen distribution adjusting method optimized by a czochralski silicon single crystal growth process of the invention;
FIG. 2(a) to FIG. 2(b) are graphs showing the solid-liquid interface oxygen concentration distribution at different superconducting magnetic field strengths in the method for optimizing the solid-liquid interface oxygen distribution regulation in the Czochralski silicon single crystal growth process of the present invention;
FIGS. 3(a) to 3(d) are graphs showing the solid-liquid interface oxygen concentration distribution at different crystal rotation speeds in the method for optimizing the solid-liquid interface oxygen distribution regulation in the Czochralski silicon single crystal growth process of the present invention;
FIGS. 4(a) to 4(d) are graphs showing the solid-liquid interface oxygen concentration distribution at different crucible rotation speeds in the method for optimizing the solid-liquid interface oxygen distribution regulation in the Czochralski silicon single crystal growth process of the present invention;
FIG. 5 is a solid-liquid interface oxygen concentration distribution curve diagram under high crystal rotation and low crucible rotation in the solid-liquid interface oxygen distribution adjusting method optimized by the czochralski silicon single crystal growth process;
FIG. 6 is a solid-liquid interface oxygen concentration distribution curve diagram under low crucible rotation and low crucible rotation in the method for adjusting the solid-liquid interface oxygen distribution optimized by the czochralski silicon single crystal growth process.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a method for adjusting oxygen distribution of an optimized solid-liquid interface of a czochralski silicon single crystal growth process, which is implemented according to the following steps:
step 1, constructing a three-dimensional local physical model required by the growth of the silicon single crystal by the Czochralski method, and specifically implementing the following steps:
step 1.1, as shown in figure 1, utilizing a Gambit software grid to generate a three-dimensional local physical model for the growth of silicon single crystals by a Czochralski method, wherein the three-dimensional local physical model comprises crystals, melts, a quartz crucible and a graphite crucible;
step 1.2, setting the radius of a quartz crucible to be 0.306m, the radius of a graphite crucible to be 0.32m, the radius of a melt in the crucible to be 0.3m, rotating the crucible anticlockwise, and setting the rotating speed of the crucible to be omegac(ii) a The radius range of the crystal is 0.15 m-0.225 m, the crystal rotates clockwise, and the rotation speed of the crystal is omegasThe height of the melt is 0.08-0.22 m, the length of the crystal is 0-0.6 m, the feeding amount is 160kg, the free interface is the interface between the silicon melt and the gas, and the solid-liquid interface is the phase interface between the crystal and the melt. Wherein, the crucible rotating speed omegac0-10 rpm, crystal rotation speed omegasIs 0 to 16 rpm. In the simulation experiment of the present invention, the crystal radius was set to 0.15m and the crystal length was set to 0.2 m.
Step 2, importing the three-dimensional local physical model into a CFX fluid simulation module, setting simulation as steady-state simulation, and setting physical parameters and superconducting magnetic field intensity of silicon melt, silicon crystal, graphite crucible and quartz crucible, wherein the physical parameters are set as shown in Table 1:
TABLE 1 physical Property parameters
Figure BDA0001403971240000101
The method is implemented according to the following steps:
step 2.1, setting the crucible to rotate anticlockwise, wherein the rotating speed of the crucible is omegacThe crystal rotates clockwise at omegas；
Step 2.2, assuming that the silicon melt is incompressible Newtonian fluid; assuming that the silicon melt satisfies the Boussinesq approximation; setting a solid-liquid interface as a flat surface, wherein a supercooled state does not occur during crystallization of the solid-liquid interface, and the temperature of the solid-liquid interface is 1685K of the melting point of silicon; setting the interface of the melt and argon, namely the free liquid level is a flat surface, the height of the free liquid level is the same as that of the solid-liquid interface, and radiating heat to the external atmosphere environment; the bottom of the quartz crucible, the inner wall of the crucible and the silicon melt meet the condition of no sliding boundary; the oxygen transport process in the melt has negligible effect on the melt flow and heat transfer,
in step 2.2, the boundary conditions used in the simulation iterative solution process include an oxygen concentration boundary condition and a temperature boundary condition, wherein the oxygen concentration boundary condition is as follows:
(1) the boundary condition of the oxygen concentration at the boundary of the silicon melt and the inner wall of the quartz crucible is as follows:
Figure BDA0001403971240000111
Figure BDA0001403971240000112
Figure BDA0001403971240000113
wherein N isAIs the alpha-Galois constant of the analog-to-digital converter,
Figure BDA0001403971240000114
is the partial pressure of oxygen, aoIs the volume fraction of oxygen, R is the oxygen gas molar constant, T is the chemical reaction temperature,
Figure BDA0001403971240000115
is a chemical reaction
Figure BDA0001403971240000116
Amount of change in free energy.
(2) Oxygen concentration boundary condition at interface of silicon melt and argon gas:
Figure BDA0001403971240000117
in the formula, COAnd CsurfThe oxygen concentration in the melt and the oxygen concentration at the free liquid level, respectively; cSiIs the silicon melt concentration; dOAnd DSiOThe diffusion coefficient of oxygen in the silicon melt and the diffusion coefficient of SiO gas in argon respectively; Δ G is the chemical reaction formula (Si)melt+Omelt＝SiOgas) Amount of change in free energy of p0Is the vapor pressure of SiO gas, R is the gas molar constant, T isThe temperature of the chemical reaction; deltagIs the free liquid level boundary layer thickness;
in the actual growth environment of the crystal, the oxygen concentration C of the free liquid surface is blown by argon gassurfOnly the internal oxygen concentration C of the meltOTen thousand of (a), thus the oxygen concentration C of the free liquid surfacesurfNeglecting, the oxygen concentration boundary condition of the free liquid surface is simplified to
CO＝0mol/m3；
(3) Oxygen concentration boundary conditions at solid-liquid interface (crystal growth interface):
Figure BDA0001403971240000121
wherein D is the diffusion coefficient of oxygen, VgThe moving speed of the solid-liquid interface, k is the segregation coefficient of oxygen, CoIs the oxygen concentration in the melt. Experiments show that the segregation coefficient of oxygen is close to unit 1, and more than 99 percent of oxygen is volatilized into argon from a free liquid surface, so that the content of oxygen doped into crystals is ignored in the whole oxygen flux balance of a solid-liquid interface, and the formula is simplified into that
Figure BDA0001403971240000122
In the temperature boundary condition, the bottom of the graphite crucible and the outer wall of the graphite crucible are applied with equal gradient temperature distribution values, and a heat flux density equation is established at the free liquid level, which is as follows:
Figure BDA0001403971240000123
Ql'＝qout,k-qin,k＝σεT4-εqin,k
qin,k＝sumj＝1～N(Fk,jqout,j)
wherein β [ T (r) -T0(r)]1.25Describing the heat loss due to gas convection, Ql' use withTo describe the heat loss of the melt level by radiation, T being the free level temperature, T0Is ambient temperature, KlFor the heat transfer coefficient of the silicon melt, β is the heat loss coefficient of gas convection, r is the free liquid surface radius, ε is the emissivity, σ is the Stefan-Boltzmann constant, Fk,jIs the angular coefficient between the two surfaces of k, j, qout,kIs the heat flow out of the surface, qin,kThe heat flow flowing into the surface is shown, x and z are direction variables of a space rectangular coordinate system, and N is the total number of the surface;
similar heat flux density equations are also established at the top surfaces of the graphite crucible and the quartz crucible, the inner surface of the quartz crucible not in contact with the silicon melt, and the solid surfaces such as the outer surface of the crystal, as follows:
Figure BDA0001403971240000131
Qs'＝qout,k-qin,k＝σεT4-εqin,k
wherein Q iss' to describe the heat loss from a solid surface by radiation, KsThe thermal conductivity of the silicon melt is shown as r, the radius of the crystal or the inner radius of the quartz crucible is shown as r, and y is a direction variable of a space rectangular coordinate system.
Setting the iteration times to 90000, the time factor to 1 and the residual error value of the convergence curve to 1E-06 in the iteration solving control;
step 3, solving the radial oxygen concentration distribution condition of the solid-liquid interface under different superconducting horizontal magnetic field strengths, and specifically implementing the following steps:
step 3.1, using a numerical solver of the CFX module to numerically solve the crystal rotation speed omega under different superconducting horizontal magnetic field strengthssAnd the rotational speed omega of the cruciblecBoth flow and heat transfer within the crucible melt at 0 rpm;
step 3.2, obtaining a temperature distribution cloud picture and an oxygen concentration distribution cloud picture of the melt through post-processing of the CFX module after iterative convergence, tracking the position of a temperature line 1685K of the solid-liquid interface on the temperature distribution cloud picture to obtain oxygen concentration distribution data on the solid-liquid interface,obtaining a relation curve of oxygen concentration and crystal diameter, i.e. a radial oxygen concentration distribution curve of the solid-liquid interface, as shown in FIG. 2, wherein FIG. 2(a) is a radial oxygen concentration distribution curve in a plane of 0 to 180 degrees (parallel to the magnetic field direction) of the solid-liquid interface, and FIG. 2(b) is a radial oxygen concentration distribution curve in a plane of 90 to 270 degrees (perpendicular to the magnetic field direction) of the solid-liquid interface, according to the average oxygen concentration of the solid-liquid interface
Figure BDA0001403971240000132
Mean square error MSE of radial oxygen concentration profileOSum gradient error sum deltaOSelecting suitable superconducting magnetic field strength for minimum principle, as shown in the following formula
Figure BDA0001403971240000133
Wherein n is the number of collected oxygen data on the solid-liquid interface, ciIs an oxygen data point, i is an oxygen data independent variable;
Figure BDA0001403971240000134
Figure BDA0001403971240000141
wherein, gradOiIs the gradient, gradO, of each oxygen data point on the solid-liquid interface radial oxygen concentration distribution curveminIs the minimum gradient, gradient error sum delta of the radial oxygen concentration distribution curve of the solid-liquid interfaceOThe smaller the oxygen concentration distribution, the more uniform the radial oxygen concentration distribution of the solid-liquid interface is;
step 4, analyzing the influence of the crystal rotation speed on the solid-liquid interface shape and the radial temperature distribution in the melt, and specifically implementing the following steps:
step 4.1, in the CFX pretreatment setting, setting the appropriate magnetic field intensity selected in the step 3, and setting the crucible rotation speed omegacSet to 0rpm, adjust different crystal rotation speeds omegasAnd iteratively solving until the residual error curve converges, thereby obtaining the temperature on the isotherm of the solid-liquid interface 1685KOxygen concentration data of (d);
step 4.2, obtaining a relation curve between the oxygen concentration and the crystal diameter, namely a solid-liquid interface radial oxygen concentration distribution curve, in order to analyze the influence of the crystal rotation speed on the solid-liquid interface shape and the melt internal radial temperature distribution, wherein the temperature detection position is taken from the inside of the melt, is 0.08m away from the melt and argon interface, the length is 0.3m, the direction is from the crucible to the melt interface to the crystal growth axis, and the graphs (a) to (d) in the figures 3 are respectively a solid-liquid interface radial oxygen concentration distribution curve in a 0-180-degree plane, a solid-liquid interface radial oxygen concentration distribution curve in a 90-270-degree plane, a solid-liquid interface shape and a melt internal temperature detection radial temperature distribution curve, according to the solid-liquid interface average oxygen concentration distribution
Figure BDA0001403971240000142
Mean square error MSE of radial oxygen concentration profileOSum gradient error sum deltaOSelecting proper crystal rotation speed as a minimum principle;
and 5, analyzing the influence of the crucible rotation speed on the solid-liquid interface shape and the radial temperature distribution in the melt, and specifically implementing the following steps:
step 5.1, in the CFX pretreatment setting, setting the magnetic field intensity to be the proper magnetic field intensity selected in the step 3, and setting the crystal rotation speed omegasIs 0rpm, the rotating speed omega of the crucible is adjustedcIteratively solving through a numerical solver until a residual error curve converges, thereby obtaining oxygen concentration data on a solid-liquid interface 1685K isotherm;
step 5.2, obtaining a relation curve between the oxygen concentration and the crystal diameter, namely a radial oxygen concentration distribution curve of the solid-liquid interface, in order to analyze the influence of the crucible rotation speed on the shape of the solid-liquid interface and the radial temperature distribution in the melt, wherein the temperature detection position is taken from the inside of the melt, the height is 0.08m away from the interface of the melt and the argon, the length is 0.3m, the direction is from the interface of the crucible and the melt to the crystal growth axis, and the graphs in the figures 4(a) to 4(d) are respectively a radial oxygen concentration distribution curve in a 0-180-degree plane of the solid-liquid interface, a radial oxygen concentration distribution curve in a 90-270-degree plane of the solid-liquid interface, and a radial temperature distribution curve at the shape of the solidAccording to the average oxygen concentration at solid-liquid interface
Figure BDA0001403971240000151
Mean square error MSE of radial oxygen concentration profileOSum gradient error sum deltaOSelecting proper crystal rotation speed as a minimum principle;
and 6, integrating the steps 3-5, and obtaining oxygen concentration distribution information of a solid-liquid interface of the czochralski silicon single crystal under the superconducting horizontal magnetic field by combining the combined action of the selected superconducting horizontal magnetic field intensity, the crystal rotating speed and the crucible rotating speed, wherein the oxygen concentration distribution information is implemented according to the following steps:
step 6.1, in the CFX pretreatment setting, setting the superconducting horizontal magnetic field intensity and the crucible rotating speed as the proper superconducting horizontal magnetic field intensity and the crucible rotating speed selected in the step 3 and the step 5, and because the high crystal rotation is favorable for improving the consistency of a solid-liquid interface, firstly, the crystal rotating speed omega is setsSetting as high crystal transition, and obtaining a solid-liquid interface radial oxygen concentration distribution curve through numerical iteration solution and MATLAB mapping, as shown in FIG. 5;
step 6.2, rotating the crystal at the speed omegasSetting the crystal transition as low crystal transition, and obtaining a solid-liquid interface radial oxygen concentration distribution curve through numerical iteration solution and MATLAB mapping, as shown in FIG. 6;
step 6.3, calculating the crystal rotation speed omega respectivelysThe average oxygen concentration of the solid-liquid interface in the radial oxygen concentration distribution curve of the solid-liquid interface at the time of high crystal transition and low crystal transition
Figure BDA0001403971240000152
And mean square error MSE associated with uniformity of oxygen concentration distributionOSum gradient error sum deltaOThrough quantitative and qualitative comparative analysis, the superconducting horizontal magnetic field intensity, the crystal rotating speed and the crucible rotating speed which are suitable for reducing the oxygen concentration of the solid-liquid interface and improving the radial oxygen concentration distribution uniformity of the solid-liquid interface are obtained through selection.
In order to research and analyze the influence of the superconducting magnetic field on the growth of the czochralski silicon single crystal, the numerical simulation model of the invention takes a TDR-120 full-automatic CZ-Si single crystal furnace of the university of Western Anlun as a prototype, and a horizontal superconducting magnetic field is added. For the convenience of numerical calculation, a part of the structure is appropriately simplified. Establishing a three-dimensional physical model in the middle growth period of the czochralski silicon single crystal, wherein the specific physical parameters comprise: the diameter of the crystal is 300mm, the feeding amount is 160kg, the length of the crystal is 200mm, the growth speed of the crystal is 0.52mm/min, the X direction is a horizontal superconducting magnetic field, the Y axis is the growth axis direction of the crystal, and the maximum superconducting magnetic induction intensity can reach 0.5T, as shown in figure 1.
The crucible is rotated to omega by a CFX fluid simulation module in numerical simulation software ANSYScAnd crystal transformation omegasSetting the speed to be 0rpm, adjusting the superconducting magnetic induction intensity to be 0.25T and 0.5T respectively, and obtaining the radial oxygen concentration distribution curve of the solid-liquid interface under different magnetic field strengths, as shown in figure 2, wherein figures 2(a) -2(b) are radial oxygen concentration distribution curves in a 0-180 degree plane and a 90-270 degree plane of the solid-liquid interface respectively. The higher the magnetic field intensity is, the lower the average oxygen concentration of the solid-liquid interface is, and the better the uniformity of the oxygen concentration is; the crucible is rotated to omegacSet at 0rpm, adjusted for crystal rotation omegasRespectively at 6rpm, 8rpm and 16rpm, and obtaining the oxygen concentration distribution information of the solid-liquid interface by iterative solution. Crystal transformation of omegasThe higher the average oxygen concentration at the solid-liquid interface, the worse the uniformity of the oxygen concentration distribution, and FIG. 3(a) to FIG. 3(d) show different crystal transitions ωsRadial oxygen concentration distribution curve in 0-180 degree plane of lower solid-liquid interface, radial oxygen concentration distribution curve in 90-270 degree plane of solid-liquid interface, solid-liquid interface shape and temperature distribution in melt, and then crystal is transformed to omegasSet to 0rpm, adjust crucible rotation omegacRespectively at 0.5rpm, 2rpm and 4rpm, and iteratively solving to obtain the solid-liquid interface oxygen concentration distribution result. Crucible rotation omegacThe higher the oxygen concentration is, the higher the oxygen concentration in the edge region of the solid-liquid interface is, the better the uniformity of the oxygen concentration becomes, and FIGS. 4(a) -4(d) are respectively different crucible rotation omegacThe radial oxygen concentration distribution curve of the lower solid-liquid interface, the shape of the solid-liquid interface and the detection temperature distribution in the melt. By comprehensively considering the principle that the oxygen concentration of the solid-liquid interface is low and the radial oxygen concentration distribution is more uniform, selecting the superconducting magnetic induction intensity of 0.5T and the crucible rotation speed of 0.5rpm, and setting the crystal rotation omegas16rpm, high crystal transition omegasLow crucible rotation omegacThe solid-liquid interface oxygen concentration distribution curve below was set at 0.5T of superconducting induction strength and 0.5rpm of crucible rotation speed, as shown in FIG. 5Crystal setting and omega turningsAt 6rpm, a low crystal transition omega was obtainedsLow crucible rotation omegacThe solid-liquid interface oxygen concentration distribution curve below is shown in FIG. 6.
In FIG. 5, the simulation results for high crystal rotation and low crucible rotation are shown respectively
Figure BDA0001403971240000171
And
Figure BDA0001403971240000172
the average oxygen concentration of the solid-liquid interface is 0-180 DEG plane and 90-270 DEG plane
Figure BDA0001403971240000173
Figure BDA0001403971240000174
Using mean square error MSE respectivelyOSum gradient error sum deltaOThe uniformity of the radial oxygen concentration distribution in the 0-180 DEG plane and the 90-270 DEG plane of the solid-liquid interface is evaluated.
(1) Using MSEOxyAnd MSEOyzRespectively shows the radial oxygen concentration distribution uniformity in a solid-liquid interface plane of 0 to 180 degrees and a plane of 90 to 270 degrees, namely
Figure BDA0001403971240000175
Figure BDA0001403971240000176
(2) Using deltaOxyAnd deltaOyzRespectively shows the radial oxygen concentration distribution uniformity in a solid-liquid interface plane of 0 to 180 degrees and a plane of 90 to 270 degrees, namely
Figure BDA0001403971240000177
Figure BDA0001403971240000178
In FIG. 6, the simulation results for low crystal rotation and low crucible rotation show the average oxygen concentration at the solid-liquid interface
Figure BDA0001403971240000179
And radial oxygen concentration distribution uniformity MSEOAnd deltaOAre respectively as
Figure BDA00014039712400001710
Figure BDA00014039712400001711
MSEOxy＝0.0073,MSEOyz＝0.0020
δOxy＝0.7316,δOyz＝0.6539
Compared with the simulation result under the process regulation of the traditional high crystal rotation and low crucible rotation, the result shows that under the process regulation method of the low crystal rotation and the low crucible rotation, the average oxygen concentration of a solid-liquid interface is lower, the radial oxygen concentration distribution uniformity of the solid-liquid interface is more uniform, and the requirement of large-size electronic grade czochralski silicon single crystal on the content of oxygen impurities in the crystal is met (
Figure BDA0001403971240000181
Magnitude).

Claims (3)

1.一种直拉硅单晶生长工艺优化固液界面氧分布调节方法，其特征在于，具体按照以下步骤实施：1. a Czochralski silicon single crystal growth process optimization method for adjusting the oxygen distribution of solid-liquid interface, is characterized in that, is specifically implemented according to the following steps: 步骤1、构建直拉法硅单晶生长所需的三维局部物理模型；Step 1. Build a three-dimensional local physical model required for the growth of Czochralski silicon single crystals; 步骤2、将三维局部物理模型导入CFX流体仿真模块，设置仿真模拟为稳态模拟，并设置硅熔体、硅晶体、石墨坩埚和石英坩埚的物性参数和超导磁场强度；Step 2. Import the 3D local physical model into the CFX fluid simulation module, set the simulation to a steady state simulation, and set the physical parameters and superconducting magnetic field strength of the silicon melt, silicon crystal, graphite crucible and quartz crucible; 步骤3、求解不同超导水平磁场强度下固液界面径向氧浓度分布情况；Step 3. Solve the radial oxygen concentration distribution at the solid-liquid interface under different superconducting horizontal magnetic field strengths; 步骤4、分析晶体转速对固液界面形状和熔体内径向温度分布的影响；Step 4. Analyze the effect of crystal rotation speed on the shape of the solid-liquid interface and the radial temperature distribution in the melt; 步骤5、分析坩埚转速对固液界面形状和熔体内径向温度分布的影响；Step 5. Analyze the influence of the crucible rotational speed on the shape of the solid-liquid interface and the radial temperature distribution in the melt; 步骤6、综合步骤3～5，结合所选取的超导水平磁场强度、晶体转速和坩埚转速三者的共同作用下，得到超导水平磁场下直拉硅单晶固液界面氧浓度分布信息；Step 6, synthesizing steps 3 to 5, combined with the combined action of the selected superconducting horizontal magnetic field strength, crystal rotational speed and crucible rotational speed, to obtain the oxygen concentration distribution information of the Czochralski silicon single crystal solid-liquid interface under the superconducting horizontal magnetic field; 所述步骤1具体按照以下步骤实施：The step 1 is specifically implemented according to the following steps: 步骤1.1、利用Gambit软件网格生成直拉法硅单晶生长的三维局部物理模型，包含晶体、熔体、石英坩埚和石墨坩埚；Step 1.1, use Gambit software grid to generate a three-dimensional local physical model of Czochralski silicon single crystal growth, including crystal, melt, quartz crucible and graphite crucible; 步骤1.2、设置石英坩埚半径为0.306m，石墨坩埚半径为0.32m，坩埚内熔体半径为0.3m，坩埚逆时针旋转，坩埚转速为ωc；晶体半径范围为0.15m～0.225m，晶体顺时针旋转，晶体转速为ωs，熔体高度为0.08m～0.22m，晶体长度为0m～0.6m，投料量160kg，自由界面为硅熔体和气体交界面，固液界面为晶体与熔体之间的相界面；Step 1.2, set the radius of the quartz crucible to 0.306m, the radius of the graphite crucible to 0.32m, the radius of the melt in the crucible to be 0.3m, the crucible to rotate counterclockwise, and the rotation speed of the crucible to be ω c ; Clock rotation, crystal rotation speed is ω s , melt height is 0.08m-0.22m, crystal length is 0m-0.6m, feeding amount is 160kg, free interface is silicon melt and gas interface, solid-liquid interface is crystal and melt interface the interface between 所述步骤2具体按照以下步骤实施：The step 2 is specifically implemented according to the following steps: 步骤2.1、设置坩埚为逆时针旋转，坩埚转速为ωc，晶体顺时针旋转，晶体转速为ωs；Step 2.1, set the crucible to rotate counterclockwise, the crucible rotation speed is ω c , the crystal rotates clockwise, and the crystal rotation speed is ω s ; 步骤2.2、假设硅熔体为不可压缩的牛顿流体；假设硅熔体满足Boussinesq近似；设置固液界面为平直面，在固液界面结晶时不发生过冷态，固液界面的温度为硅的熔点温度1685K；设置熔体与氩气交界面，即自由液面为平直面，其位置高度与固液界面高度相同，并向外界气氛环境辐射热量；石英坩埚底部和坩埚内壁与硅熔体满足无滑移边界条件；熔体内的氧输运过程对熔体流动与传热的影响忽略不计；Step 2.2. Assume that the silicon melt is an incompressible Newtonian fluid; it is assumed that the silicon melt satisfies the Boussinesq approximation; the solid-liquid interface is set as a flat surface, and no supercooling occurs during crystallization at the solid-liquid interface, and the temperature of the solid-liquid interface is the temperature of silicon. The melting point temperature is 1685K; the interface between the melt and the argon gas is set, that is, the free liquid surface is a flat surface, and its position height is the same as that of the solid-liquid interface, and it radiates heat to the external atmosphere; the bottom of the quartz crucible and the inner wall of the crucible meet the requirements of the silicon melt. No-slip boundary condition; the effect of oxygen transport in the melt on melt flow and heat transfer is negligible; 所述步骤2.2中，仿真迭代求解过程中所用到的边界条件包括有氧浓度边界条件和温度边界条件，其中氧浓度边界条件如下：In the step 2.2, the boundary conditions used in the simulation iterative solution process include oxygen concentration boundary conditions and temperature boundary conditions, wherein the oxygen concentration boundary conditions are as follows: (1)硅熔液与石英坩埚内壁交界处的氧浓度边界条件：(1) The oxygen concentration boundary conditions at the junction of the silicon melt and the inner wall of the quartz crucible:
Figure FDA0002202734290000021
Figure FDA0002202734290000021
Figure FDA0002202734290000022
Figure FDA0002202734290000022
Figure FDA0002202734290000023
Figure FDA0002202734290000023
 其中，NA为阿伏伽德罗常数，
Figure FDA0002202734290000024
为氧分压，ao为氧体积分数，R为氧气体摩尔常数，T为化学反应温度，
Figure FDA0002202734290000025
为化学反应
Figure FDA0002202734290000026
自由能变化量；where NA is Avogadro's constant,
Figure FDA0002202734290000024
is the oxygen partial pressure, a o is the oxygen volume fraction, R is the oxygen gas molar constant, T is the chemical reaction temperature,
Figure FDA0002202734290000025
for chemical reaction
Figure FDA0002202734290000026
change in free energy; (2)硅熔液与氩气交界面处的氧浓度边界条件：(2) The boundary condition of oxygen concentration at the interface between silicon melt and argon gas:
Figure FDA0002202734290000027
Figure FDA0002202734290000027
 式中，CO和Csurf分别是熔体中的氧浓度和自由液面的氧浓度；CSi是硅熔液浓度；DO和DSiO分别是氧在硅熔体中的扩散系数和SiO气体在氩气中的扩散系数；ΔG是化学反应式Simelt+Omelt＝SiOgas的自由能变化量，p0是一氧化硅气体的蒸汽压力，R为气体摩尔常数，T是化学反应温度；δg是自由液面边界层厚度；In the formula, CO and C surf are the oxygen concentration in the melt and the oxygen concentration of the free liquid surface, respectively; C Si is the silicon melt concentration; DO and D SiO are the diffusion coefficient of oxygen in the silicon melt and SiO, respectively. Diffusion coefficient of gas in argon; ΔG is the change in free energy of chemical reaction formula Si melt + O melt = SiO gas , p 0 is the vapor pressure of silicon monoxide gas, R is the gas molar constant, and T is the chemical reaction temperature ; δ g is the thickness of the free surface boundary layer; 在晶体实际生长环境过程中，自由液面的氧在氩气的吹拂下，自由液面的氧浓度Csurf仅为熔体内部氧浓度CO的万分数，因此将自由液面的氧浓度Csurf忽略不计，则自由液面的氧浓度边界条件简化为In the actual growth environment of the crystal, the oxygen in the free liquid surface is blown by argon, the oxygen concentration C surf of the free liquid surface is only ten thousand percent of the oxygen concentration C O in the melt, so the oxygen concentration C surf of the free liquid surface is If surf is ignored, the oxygen concentration boundary condition of the free surface is simplified as CO＝0mol/m3； CO =0mol/m 3 ; (3)固液界面即晶体生长界面处的氧浓度边界条件：(3) The oxygen concentration boundary condition at the solid-liquid interface, that is, the crystal growth interface:
Figure FDA0002202734290000031
Figure FDA0002202734290000031
 式中，D为氧的扩散系数，Vg为固液界面的移动速度，k为氧的分凝系数，Co为熔体内的氧浓度，实验揭示氧的分凝系数接近单位1，且超过99％的氧气从自由液面挥发到氩气当中，所以在固液界面整体氧通量平衡中将掺入到晶体中的氧含量忽略不计，上式简化为where D is the diffusion coefficient of oxygen, V g is the moving speed of the solid-liquid interface, k is the segregation coefficient of oxygen, and C o is the oxygen concentration in the melt. More than 99% of the oxygen is volatilized into the argon from the free liquid surface, so the oxygen content incorporated into the crystal is neglected in the overall oxygen flux balance at the solid-liquid interface. The above formula is simplified as
Figure FDA0002202734290000032
Figure FDA0002202734290000032
 温度边界条件中石墨坩埚底部和石墨坩埚外壁施加等梯度温度分布值，在自由液面处建立热流密度方程，如下式：In the temperature boundary condition, the constant gradient temperature distribution value is applied to the bottom of the graphite crucible and the outer wall of the graphite crucible, and the heat flux density equation is established at the free liquid surface, as follows:
Figure FDA0002202734290000033
Figure FDA0002202734290000033
 Q'l＝qout,k-qin,k＝σεT4-εqin,k Q' l =q out,k -q in,k =σεT 4 -εq in,k qin,k＝sumj＝1～N(Fk,jqout,j)q in,k =sum j=1～N (F k,j q out,j ) 式中，β[T(r)-T0(r)]1.25用来描述由于气体对流而产生的热损耗，Ql′用来描述熔体液面由辐射而产生的热损耗，T为自由液面温度，T0为环境温度，Kl为硅熔体热传导系数，β为气体对流的热损耗系数，r为自由液面半径，ε为辐射系数，σ为Stefan-Boltzmann常数，Fk,j为k,j两个表面之间的角系数，qout,k是流出表面的热流量，qin,k是流入表面的热流量，x,z为空间直角坐标系方向变量，N为表面总个数；In the formula, β[T(r)-T 0 (r)] 1.25 is used to describe the heat loss caused by gas convection, Q l ′ is used to describe the heat loss caused by radiation of the melt surface, and T is the free Liquid surface temperature, T 0 is the ambient temperature, K l is the thermal conductivity coefficient of silicon melt, β is the heat loss coefficient of gas convection, r is the radius of the free liquid surface, ε is the radiation coefficient, σ is the Stefan-Boltzmann constant, F k, j is the angle coefficient between the two surfaces of k, j, q out, k is the heat flow out of the surface, q in, k is the heat flow into the surface, x, z is the direction variable of the space Cartesian coordinate system, N is the surface The total number of; 在石墨坩埚和石英坩埚的顶表面，石英坩埚未与硅熔体接触的内表面以及晶体外表面固体表面，也建立相似的热流密度方程，如下式：On the top surfaces of the graphite crucible and the quartz crucible, the inner surface of the quartz crucible that is not in contact with the silicon melt and the solid surface of the outer surface of the crystal, a similar heat flow density equation is also established, as follows:
Figure FDA0002202734290000041
Figure FDA0002202734290000041
 Q's＝qout,k-qin,k＝σεT4-εqin,k Q' s =q out,k -q in,k =σεT 4 -εq in,k 其中，Q′s用来描述固体表面由辐射而产生的热损耗，Ks为硅熔体热传导系数，r为晶体半径或者石英坩埚的内半径，y为空间直角坐标系方向变量；Among them, Q' s is used to describe the heat loss caused by radiation on the solid surface, K s is the thermal conductivity of silicon melt, r is the crystal radius or the inner radius of the quartz crucible, and y is the direction variable of the space rectangular coordinate system; 在迭代求解控制中设置迭代次数为90000，时间因子为1，收敛曲线的残差值设置为1E-06；In the iterative solution control, set the number of iterations to 90000, the time factor to 1, and the residual value of the convergence curve to 1E-06; 所述步骤3具体按照以下步骤实施：The step 3 is specifically implemented according to the following steps: 步骤3.1、利用CFX模块的数值求解器，数值求解不同超导水平磁场强度下，晶体转速ωs和坩埚转速ωc均为0rpm时坩埚熔体内的流动与传热；Step 3.1, using the numerical solver of the CFX module, numerically solve the flow and heat transfer in the crucible melt when the crystal rotational speed ω s and the crucible rotational speed ω c are both 0 rpm under different superconducting horizontal magnetic field strengths; 步骤3.2、当迭代收敛后通过CFX模块的后处理得到熔体的温度分布云图以及氧浓度分布云图，在温度分布云图上追踪固液界面1685K等温线位置，获取固液界面上的氧浓度分布数据，得到氧浓度与晶体直径的关系曲线，即固液界面径向氧浓度分布曲线，依据固液界面平均氧浓度
Figure FDA0002202734290000042
径向氧浓度分布曲线的均方误差MSEO和梯度误差和δO为最小原则，选取合适的超导磁场强度，如下式Step 3.2. After the iteration converges, the temperature distribution cloud map and oxygen concentration distribution cloud map of the melt are obtained through post-processing of the CFX module, and the 1685K isotherm position of the solid-liquid interface is tracked on the temperature distribution cloud map to obtain the oxygen concentration distribution data on the solid-liquid interface. , the relationship curve between oxygen concentration and crystal diameter is obtained, that is, the radial oxygen concentration distribution curve at the solid-liquid interface, according to the average oxygen concentration at the solid-liquid interface
Figure FDA0002202734290000042
The mean square error MSE O and the gradient error and δ O of the radial oxygen concentration distribution curve are the minimum principles, and the appropriate superconducting magnetic field strength is selected as follows:
Figure FDA0002202734290000043
Figure FDA0002202734290000043
 其中，n为所采集到固液界面上的氧数据个数，ci为氧数据点，i为氧数据自变量；Among them, n is the number of oxygen data collected on the solid-liquid interface, ci is the oxygen data point, and i is the oxygen data independent variable;
Figure FDA0002202734290000051
Figure FDA0002202734290000051
Figure FDA0002202734290000052
Figure FDA0002202734290000052
 其中，gradOi是固液界面径向氧浓度分布曲线上各氧数据点的梯度，gradOmin是固液界面径向氧浓度分布曲线的最小梯度，梯度误差和δO越小，则说明固液界面径向氧浓度分布的均匀性越均匀；Among them, gradO i is the gradient of each oxygen data point on the radial oxygen concentration distribution curve of the solid-liquid interface, and gradO min is the minimum gradient of the radial oxygen concentration distribution curve of the solid-liquid interface. The more uniform the radial oxygen concentration distribution of the interface is; 所述步骤4具体按照以下步骤实施：The step 4 is specifically implemented according to the following steps: 步骤4.1、在CFX前处理设置中，设置磁场强度为步骤3所选取的合适磁场强度，将坩埚转速ωc设置为0rpm，调节不同晶体转速ωs，迭代求解至残差曲线收敛，从而获取固液界面1685K等温线上的氧浓度数据；Step 4.1. In the CFX preprocessing setting, set the magnetic field strength to the appropriate magnetic field strength selected in step 3, set the crucible rotational speed ω c to 0 rpm, adjust the rotational speed ω s of different crystals, and iteratively solve until the residual curve converges, thereby obtaining the solid state. The oxygen concentration data on the 1685K isotherm of the liquid interface; 步骤4.2、得到氧浓度与晶体直径之间的关系曲线，即固液界面径向氧浓度分布曲线，为了分析晶体转速对固液界面形状和熔体内径向温度分布的影响，温度检测位置取自熔体内部，距离熔体与氩气交界面0.08m，长度为0.3m，方向由坩埚与熔体交界面指向晶体生长轴，依据固液界面平均氧浓度
Figure FDA0002202734290000053
径向氧浓度分布曲线的均方误差MSEO和梯度误差和δO为最小原则，选取合适的晶体转速；Step 4.2. Obtain the relationship curve between oxygen concentration and crystal diameter, that is, the radial oxygen concentration distribution curve at the solid-liquid interface. Inside the melt, the distance from the interface between the melt and the argon gas is 0.08m, and the length is 0.3m. The direction is from the interface between the crucible and the melt to the crystal growth axis. According to the average oxygen concentration at the solid-liquid interface
Figure FDA0002202734290000053
The mean square error MSE O of the radial oxygen concentration distribution curve, the gradient error and δ O are the minimum principles, and the appropriate crystal rotation speed is selected; 所述步骤5具体按照以下步骤实施：The step 5 is specifically implemented according to the following steps: 步骤5.1、在CFX前处理设置中，设置磁场强度为步骤3所选取的合适磁场强度，设置晶体转速ωs为0rpm，调节坩埚转速ωc，通过数值求解器迭代求解至残差曲线收敛，从而获取固液界面1685K等温线上的氧浓度数据；Step 5.1. In the CFX preprocessing setting, set the magnetic field strength to the appropriate magnetic field strength selected in step 3, set the crystal rotation speed ω s to 0 rpm, adjust the crucible rotation speed ω c , and iteratively solve the residual curve through the numerical solver until the residual curve converges, so that Obtain the oxygen concentration data on the 1685K isotherm at the solid-liquid interface; 步骤5.2、得到氧浓度与晶体直径之间的关系曲线，即固液界面径向氧浓度分布曲线，为了分析坩埚转速对固液界面形状和熔体内径向温度分布的影响，温度检测位置取自熔体内部，高度距离熔体与氩气交界面为0.08m，长度为0.3m，方向由坩埚与熔体交界面指向晶体生长轴，依据固液界面平均氧浓度
Figure FDA0002202734290000061
径向氧浓度分布曲线的均方误差MSEO和梯度误差和δO为最小原则，选取合适的晶体转速。Step 5.2. Obtain the relationship curve between oxygen concentration and crystal diameter, that is, the radial oxygen concentration distribution curve at the solid-liquid interface. Inside the melt, the height is 0.08m from the interface between the melt and the argon gas, and the length is 0.3m. The direction is from the interface between the crucible and the melt to the crystal growth axis. According to the average oxygen concentration at the solid-liquid interface
Figure FDA0002202734290000061
The mean square error MSE O of the radial oxygen concentration distribution curve, the gradient error and δ O are the minimum principles, and the appropriate crystal rotation speed is selected. 2.根据权利要求1所述的一种直拉硅单晶生长工艺优化固液界面氧分布调节方法，其特征在于，所述步骤1.2中坩埚转速ωc为0～10rpm，晶体转速ωs为0～16rpm。2. The method for adjusting the oxygen distribution at the solid-liquid interface for optimizing a Czochralski silicon single crystal growth process according to claim 1, wherein in the step 1.2, the crucible rotational speed ω c is 0 to 10 rpm, and the crystal rotational speed ω s is 0～16rpm. 3.根据权利要求1所述的一种直拉硅单晶生长工艺优化固液界面氧分布调节方法，其特征在于，所述步骤6具体按照以下步骤实施：3. a kind of Czochralski silicon single crystal growth process optimization method for adjusting solid-liquid interface oxygen distribution according to claim 1, is characterized in that, described step 6 is specifically implemented according to the following steps: 步骤6.1、在CFX前处理设置中，设置超导水平磁场强度和坩埚转速为步骤3、步骤5所选取的合适超导水平磁场强度和坩埚转速，由于高晶转有利于提高固液界面的一致性，所以首先将晶体转速ωs设置为高晶转，通过数值迭代求解和MATLAB作图得到固液界面径向氧浓度分布曲线；Step 6.1. In the CFX pretreatment settings, set the superconducting horizontal magnetic field strength and crucible rotation speed to the appropriate superconducting horizontal magnetic field strength and crucible rotation speed selected in Step 3 and Step 5, because high crystal rotation is conducive to improving the consistency of the solid-liquid interface Therefore, first set the crystal rotation speed ω s to a high crystal rotation speed, and obtain the radial oxygen concentration distribution curve of the solid-liquid interface through numerical iterative solution and MATLAB drawing; 步骤6.2、将晶体转速ωs设置为低晶转，通过数值迭代求解和MATLAB作图得到固液界面径向氧浓度分布曲线；Step 6.2, set the crystal rotation speed ω s to low crystal rotation, and obtain the radial oxygen concentration distribution curve of the solid-liquid interface through numerical iterative solution and MATLAB drawing; 步骤6.3、分别计算晶体转速ωs为高晶转和低晶转时固液界面径向氧浓度分布曲线中固液界面的平均氧浓度
Figure FDA0002202734290000062
和与氧浓度分布均匀性相关的均方误差MSEO和梯度误差和δO，通过定量和定性的对比分析，选取得到既适合降低固液界面氧浓度又能提高固液界面径向氧浓度分布均匀性的超导水平磁场强度、晶体转速和坩埚转速。Step 6.3. Calculate the crystal rotation speed ω s respectively as the average oxygen concentration at the solid-liquid interface in the radial oxygen concentration distribution curve of the solid-liquid interface when the crystal rotation is high and the crystal rotation is low
Figure FDA0002202734290000062
and the mean square error MSE O and gradient error and δ O , which are related to the uniformity of the oxygen concentration distribution, through quantitative and qualitative comparative analysis, the selected results are suitable for both reducing the oxygen concentration at the solid-liquid interface and improving the radial oxygen concentration distribution at the solid-liquid interface. Uniformity of superconducting horizontal magnetic field strength, crystal rotational speed and crucible rotational speed.
CN201710811360.3A 2017-09-11 2017-09-11 Method for optimizing solid-liquid interface oxygen distribution regulation in Czochralski silicon single crystal growth process Active CN107747122B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710811360.3A CN107747122B (en) 2017-09-11 2017-09-11 Method for optimizing solid-liquid interface oxygen distribution regulation in Czochralski silicon single crystal growth process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710811360.3A CN107747122B (en) 2017-09-11 2017-09-11 Method for optimizing solid-liquid interface oxygen distribution regulation in Czochralski silicon single crystal growth process

Publications (2)

Publication Number Publication Date
CN107747122A CN107747122A (en) 2018-03-02
CN107747122B true CN107747122B (en) 2020-03-31

Family

ID=61255668

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710811360.3A Active CN107747122B (en) 2017-09-11 2017-09-11 Method for optimizing solid-liquid interface oxygen distribution regulation in Czochralski silicon single crystal growth process

Country Status (1)

Country Link
CN (1) CN107747122B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108914201B (en) * 2018-08-29 2019-09-27 西安理工大学 A Method for Optimizing Process Parameters of Czochralski Silicon Single Crystal Growth Process
CN109576785A (en) * 2018-12-29 2019-04-05 徐州鑫晶半导体科技有限公司 The method of oxygen content during adjusting monocrystalline silicon growing
CN110512278A (en) * 2019-09-12 2019-11-29 西安奕斯伟硅片技术有限公司 A kind of crystal pulling apparatus, device and method
CN111926384B (en) * 2020-06-05 2022-06-17 徐州鑫晶半导体科技有限公司 Single crystal furnace, method for determining operating parameters of single crystal furnace in growth process of single crystal silicon and method for preparing single crystal silicon
CN118658570B (en) * 2024-08-19 2024-12-06 西安交通大学 Method and device for determining shape of inner wall surface of crucible for growing silicon carbide by liquid phase method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101923591A (en) * 2010-08-09 2010-12-22 西安理工大学 Three-dimensional optimization design method of asymmetric hook-shaped magnetic field for MCZ single crystal furnace
CN103678890A (en) * 2013-11-28 2014-03-26 西北工业大学 Method for simulating influence of heating technology on premelting and melting of crystal boundaries by aid of crystal phase-field process

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7282094B2 (en) * 2003-05-28 2007-10-16 Sumco Corporation Method of simulation with respect to density distribution and size distribution of void defect within single crystal and oxygen precipitation nucleus within single crystal

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101923591A (en) * 2010-08-09 2010-12-22 西安理工大学 Three-dimensional optimization design method of asymmetric hook-shaped magnetic field for MCZ single crystal furnace
CN103678890A (en) * 2013-11-28 2014-03-26 西北工业大学 Method for simulating influence of heating technology on premelting and melting of crystal boundaries by aid of crystal phase-field process

Also Published As

Publication number Publication date
CN107747122A (en) 2018-03-02

Similar Documents

Publication Publication Date Title
CN107747122B (en) Method for optimizing solid-liquid interface oxygen distribution regulation in Czochralski silicon single crystal growth process
Zhang et al. Effect of crucible rotation and crystal rotation on the oxygen distribution at the solid-liquid interface during the growth of Czochralski monocrystalline silicon under superconducting horizontal magnetic field
EP2385025B1 (en) Method for calculating temperature distribution in crucible
Li et al. Effects of argon flow on impurities transport in a directional solidification furnace for silicon solar cells
Yang et al. A modified vacuum directional solidification system of multicrystalline silicon based on optimizing for heat transfer
Yu et al. Local design of the hot-zone in an industrial seeded directional solidification furnace for quasi-single crystalline silicon ingots
Dumitrica et al. Numerical studies on a type of mechanical stirring in directional solidification method of multicrystalline silicon for photovoltaic applications
Liu et al. Numerical investigation of carbon contamination during the melting process of Czochralski silicon crystal growth
Chen et al. Numerical simulation of the oxygen concentration distribution in silicon melt for different crystal lengths during Czochralski growth with a transverse magnetic field
Liu et al. Global simulation of coupled oxygen and carbon transport in an industrial directional solidification furnace for crystalline silicon ingots: Effect of crucible cover coating
Zhang et al. Nucleation and bulk growth control for high efficiency silicon ingot casting
Bellmann et al. A novel method for gas flow and impurity control in directional solidification of multi-crystalline silicon
WO2022268099A1 (en) Single crystal growth method and apparatus, and single crystal
Ding et al. The influence mechanism of melt flow instability on the temperature fluctuation on the crystal/melt interface during Czochralski silicon crystal growth
Jana et al. A numerical simulation study for the Czochralski growth process of Si under magnetic field
Bellmann et al. Dynamic simulation of impurity transport and chemical reactions in a Bridgman furnace for directional solidification of multi-crystalline silicon
Su et al. Numerical analysis and optimization of gas flow and impurity control in directional solidification multi-crystalline Si
Zhao et al. Effect of heater structure on oxygen concentration in large diameter n-type Czochralski silicon study using numerical simulation
Teng et al. Numerical analysis of solid–liquid interface shape during large-size single crystalline silicon with Czochralski method
Dezfoli Optimizing cooling strategies in the Czochralski process for large-diameter silicon ingots
Huang et al. Study on the effect of melt flow behavior on the uniformity of phosphorus doping during the growth of large-size n-type monocrystalline silicon by Czochralski method
Popescu et al. Numerical study of the influence of melt convection on the crucible dissolution rate in a silicon directional solidification process
Kesavan et al. Optimizing oxygen impurities using different heater design in the directional solidification of multi-crystalline silicon
Kakimoto Development of crystal growth technique of silicon by the Czochralski method
Vizman et al. Novel method for melt flow control in unidirectional solidification of multi-crystalline silicon

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20200806

Address after: E2-002, Science Park, Xi'an University of technology, No.26, gazeng Road, Zhangba Street office, hi tech Zone, Xi'an City, Shaanxi Province

Patentee after: Xi'an yisiwei Equipment Technology Co.,Ltd.

Address before: 710077 Shaanxi city of Xi'an province high tech Zone gazelle Road No. 26

Co-patentee before: Xi'an core magnetic intelligent technology partnership (limited partnership)

Patentee before: Xi'an Polytechnic Asset Management Co.,Ltd.

Effective date of registration: 20200806

Address after: 710077 Shaanxi city of Xi'an province high tech Zone gazelle Road No. 26

Co-patentee after: Liu Ding

Patentee after: Xi'an Polytechnic Asset Management Co.,Ltd.

Co-patentee after: Zhao Yue

Co-patentee after: Jiao Shangbin

Co-patentee after: Jiang Lei

Co-patentee after: Liang Yanming

Co-patentee after: Wu Shihai

Co-patentee after: Jiang Jian

Address before: 710077 Shaanxi city of Xi'an province high tech Zone gazelle Road No. 26

Patentee before: Xi'an Polytechnic Asset Management Co.,Ltd.

Effective date of registration: 20200806

Address after: 710077 Shaanxi city of Xi'an province high tech Zone gazelle Road No. 26

Patentee after: Xi'an Polytechnic Asset Management Co.,Ltd.

Address before: 710048 Shaanxi city of Xi'an Province Jinhua Road No. 5

Patentee before: XI'AN University OF TECHNOLOGY

Effective date of registration: 20200806

Address after: 710077 Shaanxi city of Xi'an province high tech Zone gazelle Road No. 26

Co-patentee after: Xi'an core magnetic intelligent technology partnership (limited partnership)

Patentee after: Xi'an Polytechnic Asset Management Co.,Ltd.

Address before: 710077 Shaanxi city of Xi'an province high tech Zone gazelle Road No. 26

Co-patentee before: Liu Ding

Patentee before: Xi'an Polytechnic Asset Management Co.,Ltd.

Co-patentee before: Zhao Yue

Co-patentee before: Jiao Shangbin

Co-patentee before: Jiang Lei

Co-patentee before: Liang Yanming

Co-patentee before: Wu Shihai

Co-patentee before: Jiang Jian

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20210924

Address after: 710000 room 1-3-029, No. 1888, Xifeng South Road, high tech Zone, Xi'an, Shaanxi Province

Patentee after: Xi'an yisiwei Material Technology Co.,Ltd.

Patentee after: Xi'an yisiwei Equipment Technology Co.,Ltd.

Address before: 710077 Science Park, Xi'an University of technology ez-002, No. 26, gazelle Road, Zhangba Street office, high tech Zone, Xi'an, Shaanxi Province

Patentee before: Xi'an yisiwei Equipment Technology Co.,Ltd.

CP01 Change in the name or title of a patent holder
CP01 Change in the name or title of a patent holder

Address after: 710000 room 1-3-029, No. 1888, Xifeng South Road, high tech Zone, Xi'an, Shaanxi Province

Patentee after: Xi'an Yisiwei Material Technology Co.,Ltd.

Patentee after: Xi'an Xinhui Equipment Technology Co.,Ltd.

Address before: 710000 room 1-3-029, No. 1888, Xifeng South Road, high tech Zone, Xi'an, Shaanxi Province

Patentee before: Xi'an yisiwei Material Technology Co.,Ltd.

Patentee before: Xi'an yisiwei Equipment Technology Co.,Ltd.