Research Article |
Corresponding author: Anatoly I. Prostomolotov ( aprosto@inbox.ru ) © 2024 Nataliya A. Verezub, Anatoly I. Prostomolotov.
This is an open access article distributed under the terms of the Creative Commons Attribution License (CC BY 4.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.
Citation:
Verezub NA, Prostomolotov AI (2024) Growth chamber gas dynamics in Cz silicon single crystal growth process. Modern Electronic Materials 10(3): 185-193. https://doi.org/10.3897/j.moem.10.3.140627
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Mathematical simulation results for inert gas (argon) dynamics in the rarefied atmosphere of Redmet-10 Cz single crystal silicon growth furnace chamber have been reported. Gas flows in cold (room temperature) and hot (growth process) chambers have been analyzed. Convective gas flows have been considered for two growth chamber gas supply options: basic supply, i.e., through the top central inlet hole only, and combined, i.e., with additional gas supply through the lateral inlet hole. Gas outlet is through the growth chamber bottom outlet hole for both options. For the cold chamber option, forced convection has been studied using the incompressible ideal gas model. For hot chamber, both the nonisothermal compressible ideal gas model and the weakly compressible gas model in the Boussinesq approximation have been used for studying the vortex structure produced by a joint action of forced and thermal-gravitational convection. The effect of different gas inlet methods on the convective transport of silicon monoxide evaporating from the free melt surface has been discussed.
Czochralski method, gas dynamics, argon, modeling, silicon monoxide
Silicon single crystals are grown using the Czochralski method at a reduced pressure in an inert gas (argon) atmosphere for avoiding or minimizing the effect of accompanying chemical reactions on the process. One important chemical reaction occurs in the silicon melt due to the dissolution of the quartz crucible resulting in the formation of silicon monoxide. The vapor-gas mixture of argon with silicon and carbon monoxides produces coagulated microparticles that deposit on the inner components of the growth chamber thus reducing their service life. The concentration of silicon monoxide in the vapor-gas mixture above the melt surface affects the intensity of its evaporation from the melt thus changing the oxygen content in the growing single crystal. Therefore studying gas dynamics in the growth chamber is important.
Publications on the topic can be divided in three groups: theoretical ones that are based on the physical representation of mass exchange during crystallization, calculations on the basis of mathematical models that may have different degrees of completeness, and technological studies the novel results of which are disclosed in patents on growth chamber gas dynamics control.
Monographs [
The intensity of crucible dissolution and oxygen transfer to the melt depends on the crucible and melt contact surface, crucible inner surface condition and convection flows in the melt. Volatile silicon monoxide SiO forms on the free melt surface and evaporates to the growth chamber space. It is recommended to accelerate this evaporation by blowing the melt surface with an inert gas (argon). Technological problems caused by oxygen and carbon contamination of silicon single crystals were addressed in [
The formation of a vapor-gas mixture of cold argon, hot silicon monoxide SiO, carbon monoxide CO and other volatile compounds above the melt in the chamber causes their coagulation in microparticles that deposit onto relatively cold inner chamber surfaces or are transferred by convective flows in the chamber space to the melt surface and enter the crystallization region thus interrupting the growth of dislocation-free single crystals.
The second group of works includes reports on the mathematical simulation of gas dynamics for different Cz growth chamber designs and various gas flow intake and outlet options. A growth chamber design was presented [
The third group of works includes patents and technical reports describing design and gas inlet/outlet novelties and changes in growth chamber fittings and materials.
The latter group includes US Patents [
RU Patent [
Technical publication [
This work deals with the innovative additional lateral gas supply method suggested in the above-cited earlier work [
The growth chamber design of the Redmet-10 industrial growth furnace for Cz silicon single crystal growth is shown in Fig.
(a) To the left of the axis: Redmet-10 furnace growth chamber components. (1) water-cooled steel shell, (2) silicon single crystal, (3) silicon melt, (4) crystallization front, (5) melt free surface, (6) quartz crucible, (7) graphite crucible support, (8) resistive heater, (9) graphite screen, (10) top central gas inlet port, (11) additional lateral gas inlet hole, (12) bottom central gas outlet hole. White arrows show gas inlet and outlet directions, black arrow shows crystal pulling direction from melt at speed V. To the right of the axis: triangle components calculation grid; (b) Knudsen number (Kn) for argon as a function of static pressure (p, torr). Symbols show earlier data [
The crystal is grown in a rarefied atmosphere at 14 torr. The argon is blown downwards (main supply) and in combination with lateral inlet (additional supply). The gas flow rate is substantially below the speed of sound (e.g. the speed of sound in argon gas is 319 m/s at 273 K). For rarefied gas dynamics, it is of fundamental importance to know the ratio of the free path length of gas molecules between collisions l and the effective flow size L, i.e., the Knudsen number: Kn = l/L.
Classical gas dynamics rules hold for Kn << 1 since in this case the gas parameters change but slightly within the free path length, and collisions between molecules produce, in the vicinity of each collision point, a local close-to-equilibrium state that can be described by the macroscopic parameters of density, speed and temperature. One can therefore represent the gas as a continuous media having the thermophysical properties of viscosity, heat conductivity, diffusion etc. According to earlier data [
The mathematical simulation of heat and mass transfer for the Cz process was carried out using the Crystmo/Marc software package [
At the first stage, the conjugate heat exchange in the crystal-melt system and at the solid components of the growth chamber was calculated in accordance with an earlier method [
At the second stage the Crystmo/Marc software package was added with two transient equation solution modules describing the flow and heat exchange on the basis of the ideal gas model [
The mass conservation equation and the moment, heat and impurity transfer equations for gases are written as follows:
– the mass conservation equation:
(1)
– the moment transfer equation for ideal gas:
(2)
– the moment transfer equation in the Boussinesq approximation for which the constant gas density ρ0 is set in accordance with the gas rarefaction level and the local temperature change is low in comparison with the reference value T0 from which local temperature is counted, i.e., (T – T0) << T0:
(3)
where τ is the tensor of stress which is deemed to be uniform and spatially isotropic, and there is a linear dependence between the tensor of stress and the tensor of strain rate:
– the heat transfer equation:
(4)
– the impurity transfer equation:
(5)
Here v is the velocity, ρg is the gravity force, µ is the dynamic viscosity coefficient, λ is the heat conductivity coefficient, cp is the heat capacity coefficient, l is a unity tensor, g is the gravity vector, C is the molecular concentration and D is the molecular diffusion coefficient of SiO in the gas.
For Eqs. (1)–(3) the velocity boundary conditions corresponded to the condition of gas sticking to solid surfaces and the inlet/outlet flow rates at the inlet and outlet holes. The temperature boundary conditions in Eq. (4) were set as described above, i.e., based on the solution of the conjugate thermal task without account for gas dynamics, and then corrected by iteration until establishment.
For the oxygen impurity transfer model in silicon melt, it was assumed that the quartz crucible is dissolved: in the melt, released molecular oxygen is trapped by the growing crystal at the crystallization front, and on the free melt surface, oxygen in the form of silicon monoxide evaporates to the gas atmosphere. For studying the effect of different gas flow convection modes on silicon monoxide transfer in the growth chamber, it is accepted that, as a result of inner processes in the melt, the silicon monoxide concentration on the melt surface reaches C0 [
The calculations were carried out in this work both for the ideal gas model and for the Boussinesq model. Comparison between the respective calculation results did not reveal any qualitative differences in the gas flow structure, isotherm distributions and silicon monoxide transfer in the growth chamber. Below is a detailed discussion of the Boussinesq model calculation results.
The physical parameters of argon gas were assumed to be linearly dependent on temperature, i.e., μ = μ(T), λ = λ(T), cp = cp (T). Note that the equation of state for ideal gas is applied to an equilibrium condition of a system of non-interacting particles, although the heat conductivity coefficient describes the non-equilibrium process of thermal balance establishment and viscosity describes molecular interactions. Viscosity and heat conductivity are described using the Chapman–Enskog kinetic theory of gases based on the Leonard–Jones molecular interaction potentials. The heat conductivity, dynamic viscosity and specific heat capacity coefficients were set linearly dependent on temperature in accordance with reference data on thermophysical values [
For the Boussinesq model, it is important to know the volume heat expansion coefficient of the gas. Its value is calculated by substituting the ideal gas equation of state into the definition of the volume heat expansion coefficient:
For example, at T = 1000 K, the following value is obtained: βT = 1/T = 10-3 1/K. The density of argon at p = 14 torr and T = 1000 K can also be evaluated from the equation of state:
In accordance with the kinetic theory, the temperature and pressure dependences of the silicon monoxide diffusion coefficient can be written as follows:
D = aT1.5/p,
where a = 3.42∙10-3 torr∙cm2/(s∙K1.5) and D = 7.73 cm2/s at T = 1000 K and p = 14 torr. Note that the SiO diffusion coefficient in argon was set using the following expression [
D = bT1.75/p,
where b = 8.626∙10-2 torr∙cm2/(s∙K1.5), which at T = 1000 K and p = 14 torr yields a value close to the above one: D = 2.09 cm2/s.
By way of example, Table
Density | Heat capacity coefficient | Heat conductivity coefficient | Dynamic viscosity coefficient | Heat expansion coefficient | SiO diffusion coefficient |
ρ (g/cm3) | cp (erg/(g∙K)) | λ (erg/(cm∙s∙K)) | μ (P) | βT (1/K) | D (cm2/s) |
8.94∙10-6 | 5.2∙106 | 2500 | 5.02∙10-4 | 10-3 | 7.73 |
Below two gas flow cases are considered: (1) in a cold growth chamber (at room temperature) and (2) in a heated growth chamber (under conditions of growing a silicon single crystal). Calculation results for silicon monoxide concentration are analyzed for the second case. The gas flow in the growth chamber is calculated for both options in the assumption of gas inlet only from the top central inlet hole at a 200 cm/s flow rate (38 sl/min) and for additional gas inlet from the lateral chamber inlet hole at the rate Vin-lat = 10 cm/s.
The main gas supply through a small (2 cm diam.) top central inlet hole for cold growth chamber (Fig.
If gas is additionally supplied through 0.9 cm diam. lateral inlet holes (Fig.
Heat release from the heater causes heat radiation towards other growth chamber components: the crystal, the crucible assembly with melt, the heat screens, the chamber walls etc. Thermal-gravitational convection occurs in the gravity field of the melt and the gas atmosphere. We consider the effect of that convection on the forced gas flow as described in the previous section.
It is of interest to make a criterion-based estimation of the effects of thermal-gravitational and forced (gas inlet) convection. In accordance with the Table
Thermal-gravitational convection has a penetrating nature. It generates a vortex above the top heater surface and the crucible assembly between which radiation heat exchange is established. This vortex propagates upwards, covers the entire top part of the chamber adjacent to the chamber side wall and changes the direction of the jet from the top central inlet hole (Fig.
Figure
A more detailed illustration of the gas dynamic parameters for the two options of chamber (Fig.
Central gas inlet in hot growth chamber at Vin = 200 cm/s: (a) gas flow, (b) isotherms and (c) silicon monoxide concentration contourlines (C/C0)
Central and lateral gas inlet in hot growth chamber at Vin = 200 cm/s: (a) gas flow, (b) isotherms and (c) silicon monoxide concentration contourlines (C/C0)
Silicon monoxide concentration (a) and gas velocity modulus (b) distributions in r = 4 cm section of hot growth chamber for two gas inlet options: (solid curves) sole central gas inlet at Vin = 200 cm/s and (dashed curves) combined (central and lateral) gas inlet at Vin = 200 cm/s and Vin-lat = 10 cm/s
The above presented review suggests that the gas dynamics problem for Cz single crystal silicon growth is actual and practically important. Along with theoretical analysis of the physicochemical processes in the growth chamber gas atmosphere, mathematical simulation taking into account the main features of the physical processes and the growth chamber design is also important. One should however point out that conjugate simulations carried out in foreign publications deal with foreign growth furnaces (EKZ-1300 or newer) having specific arrangement and assembly of the heat screens, gas inlet and outlet holes etc. For example, the space above the heater can be covered with a horizontal screen that potentially suppresses the effect of thermal-gravitational convection. That is probably why the cited foreign publications do not contain analysis of the effect of thermal-gravitational convection on the gas flow, although gas flows through high temperature gradient regions. The review presented herein also shows that some RU Patents and technical publications are based on quite simplified and sometimes inadequate understanding of gas flows.
This publication gives way to expand the knowledge of gas dynamic processes for the example of the domestic Redmet-10 furnace growth chamber. Analysis of publications devoted to the calculation of gas dynamics with gas inlet in the upper dome of the growth chamber [
The advantages of introducing gas into the growth chamber from the bottom up are discussed in the Russian patent [
The study was supported by the Government program (contract No. 124013000674-0).