WO2009154037A1 - 窒素原子測定方法、窒素原子測定装置、及びプラズマ処理装置 - Google Patents
窒素原子測定方法、窒素原子測定装置、及びプラズマ処理装置 Download PDFInfo
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- WO2009154037A1 WO2009154037A1 PCT/JP2009/057758 JP2009057758W WO2009154037A1 WO 2009154037 A1 WO2009154037 A1 WO 2009154037A1 JP 2009057758 W JP2009057758 W JP 2009057758W WO 2009154037 A1 WO2009154037 A1 WO 2009154037A1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0011—Sample conditioning
- G01N33/0013—Sample conditioning by a chemical reaction
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- the present invention relates to a nitrogen atom measuring method for measuring nitrogen atoms near atmospheric pressure, a nitrogen atom measuring apparatus for measuring nitrogen atoms, and a plasma processing apparatus using the same.
- remote plasma treatment has been widely used in which radicals generated by discharge are transported and brought into contact with an object to form an oxide film, a nitride film, etc., surface cleaning, and sterilization.
- many plasma treatments operate under reduced pressure, but in recent years, treatments near atmospheric pressure that do not require a vacuum hermetic container have attracted attention.
- remote plasma processing near atmospheric pressure is used for cleaning the surface of materials, improving wettability, film formation, and the like.
- nitrogen radicals are generated by nitrogen discharge in the vicinity of atmospheric pressure, or by discharge using a mixed gas of nitrogen and a rare gas, and a nitride film is formed by remote plasma treatment.
- the main players in the reaction are electrically neutral nitrogen radicals, especially nitrogen atoms, and grasping the density is an important issue.
- high pressure such as near atmospheric pressure
- the lifetime of nitrogen atoms is extremely short, and it is greatly attenuated in milliseconds to tens of milliseconds. For this reason, it is difficult to measure the density of nitrogen atoms, and a technique has been adopted in which optimum processing conditions are found empirically by adjusting the discharge power and the distance to the processing target.
- Patent Document 1 As a typical conventional nitrogen atom density measurement method, (1) an absorption measurement method for irradiating light of a specific wavelength and obtaining a nitrogen atom density from the attenuation of the light intensity (see, for example, Patent Document 1), (2 ) A nitric oxide gas titration method (for example, Non-Patent Document 1) in which nitrogen monoxide (hereinafter referred to as NO) gas is added to the discharge downstream gas, and the change in light emission due to the balance between the supplied NO amount and the nitrogen atom amount is measured. For example).
- NO nitrogen monoxide
- the nitrogen atom measurement method of the absorption measurement method will be described.
- the nitrogen atom density measurement method of the absorption measurement method light having a wavelength corresponding to the excitation level of nitrogen atoms (for example, wavelength of 120 nm) is generated by an atomic light generator and irradiated to a gas containing nitrogen atoms to be measured.
- the irradiated light is absorbed according to the nitrogen atom density in the measurement target gas, and the light intensity is attenuated. Therefore, the nitrogen atom density can be calculated in real time by comparing the light intensity before passing through the measurement object and the light intensity after passing through the measurement object.
- the reaction of the reaction formula (1) proceeds very rapidly and reaches equilibrium at about 1 millisecond at room temperature and near atmospheric pressure.
- Oxygen atoms (hereinafter referred to as O atoms) generated in the reaction formula (1) are consumed in the reaction of the reaction formula (2) or the reaction formula (3) depending on the amount of nitrogen atoms and the amount of NO. .
- Transition of reaction formula (2) and reaction formula (3) occurs in a region (titration point) where the amount of nitrogen atoms and the amount of NO are equal, and the luminescence distribution changes. Therefore, if the titration point is found by changing the NO supply amount and measuring the emission spectrum, the nitrogen atom density can be calculated from the supply NO amount at that time.
- the nitrogen atom density measurement method of the absorption measurement method can measure the nitrogen atom density in real time, it is generally assumed to be used under reduced pressure and is difficult to apply to the measurement near atmospheric pressure. This is because, under conditions where the particle density is high, such as in the vicinity of atmospheric pressure, scattering and attenuation of the irradiated light become significant, and the absorption intensity by the nitrogen atoms to be measured becomes relatively small.
- the nitrogen atom density measurement method of the nitric oxide gas titration method can measure nitrogen atom density relatively easily near atmospheric pressure, but it is necessary to find the titration point by changing the NO supply amount. Therefore, real-time measurement cannot be realized.
- An object of the present invention is to provide a nitrogen atom measuring method for measuring nitrogen atom density in real time near atmospheric pressure, a nitrogen atom measuring apparatus to which the nitrogen atom measuring method is applied, and a plasma processing apparatus equipped with the nitrogen atom measuring apparatus. .
- the nitrogen atom measurement method is a nitrogen atom measurement method for measuring the density of nitrogen atoms in the vicinity of atmospheric pressure, and the nitrogen atom is contained in a predetermined amount of a nitrogen atom-containing gas generated in a nitrogen atom generation source. Downstream of the generation source, after mixing the predetermined amount of nitric oxide gas having a known concentration and the reaction of the nitrogen monoxide gas mixed with the nitrogen atom-containing gas, the density of nitrogen monoxide and nitrogen dioxide The procedure for measuring the density and the relationship that the nitrogen atom density is the difference obtained by subtracting the sum of the measured concentration of nitrogen monoxide and the measured concentration of nitrogen dioxide from the known concentration of the nitric oxide gas. And calculating the nitrogen atom density using
- the nitrogen atom measuring apparatus is a nitrogen atom measuring apparatus that measures the density of nitrogen atoms in the vicinity of atmospheric pressure, and the nitrogen atom is contained in a predetermined amount of a nitrogen atom-containing gas generated in a nitrogen atom generation source.
- a plasma processing apparatus is a plasma processing apparatus that performs processing by bringing a nitrogen atom-containing gas into contact with an object to be processed.
- the plasma processing apparatus includes the nitrogen atom measuring apparatus according to the present invention, and the nitrogen atom density is predetermined.
- Control means for controlling at least one of discharge power, gas composition, gas flow, gas temperature, and gas pressure is provided so as to achieve density.
- the effect of the nitrogen atom measurement method according to the present invention is that nitrogen monoxide after mixing a predetermined amount of nitrogen monoxide gas having a known concentration with the nitrogen atom-containing gas and reacting the nitrogen atom-containing gas with the nitrogen monoxide gas.
- the nitrogen atom density is determined by measuring the density of nitrogen dioxide and the known density of the mixed nitric oxide gas and the measured density of nitrogen monoxide and nitrogen dioxide. Can be measured in real time.
- Embodiment 1 the number density (cm ⁇ 3 ) of the particle type X is expressed using the notation [X].
- concentration C X ppm.
- N A has an Avogadro number of 6.02 ⁇ 10 23 (mol ⁇ 1 ).
- the number density and density are converted as necessary.
- the supply number density of the particle type X is expressed using the notation [X] in
- the measured number density of the particle type X is expressed using the notation [X] m .
- the vicinity of the atmospheric pressure is in the range of an absolute pressure of 50 kPa to 200 kPa.
- FIG. 1 is a block diagram showing a configuration of a nitrogen atom measuring apparatus to which a nitrogen atom measuring method according to Embodiment 1 of the present invention is applied.
- a nitrogen atom-containing gas is generated by the nitrogen gas supply source 1, the flow rate controller 2a that is a nitrogen gas flow rate adjusting means, and the near-atmospheric pressure discharge unit 3. And transported by the transport pipe 10.
- the nitrogen gas supply source 1 supplies pure nitrogen gas or a gas in which nitrogen gas and rare gas are mixed at a predetermined ratio.
- the near-atmospheric-pressure discharge unit 3 includes a pair of electrodes and is connected to a high voltage power source 4.
- the nitrogen atom measuring unit includes a NO gas supply source 5, a flow rate controller 2b that is a NO gas flow rate adjusting means, a pump 6 that is a means for sucking a part of the nitrogen atom containing gas, and a flow rate adjustment of the nitrogen atom containing gas. It comprises a flow rate controller 2c as means and a nitrogen oxide concentration meter 7 for measuring NO and NO 2 concentrations.
- NO gas supply source 5 NO gas diluted to a predetermined concentration with nitrogen gas or rare gas is supplied.
- the gas intake point 9 is located downstream of the discharge unit 3 near atmospheric pressure, and the measurement gas transport pipe 11 is branched at the gas intake point 9.
- the NO gas mixing point 8 exists in the measurement gas transport pipe 11, and the flow rate controller 2 c and the nitrogen oxide concentration meter 7 are both located downstream of the NO gas mixing point 8 in the measurement gas transport pipe 11.
- Nitrogen atoms are extremely active and can be used for various purposes such as nitride film formation.
- nitrogen atoms have a very short life under high pressure, such as near atmospheric pressure, and are greatly attenuated in several milliseconds to several tens of milliseconds.
- the subject of this invention is providing the method and measuring apparatus which measure the density of nitrogen atoms of such a short life in a simple method and in real time. Moreover, it is providing the plasma processing apparatus controlled with high precision using the measuring method.
- the principle of nitrogen atom density measurement according to the present invention is that NO gas with known density is mixed with nitrogen atom-containing gas with unknown density, and the component density after the reaction between nitrogen atoms and NO reaches equilibrium is measured. Thus, the nitrogen atom density is calculated.
- the nitrogen atom reacts very rapidly with NO to generate a nitrogen molecule and an O atom.
- the O atoms generated here further react with nitrogen atoms, NO, etc. to produce other products.
- the reaction of the mixed system of nitrogen atom-containing gas and NO gas is complicated.
- the nitrogen atom density can be calculated from the supplied NO density and the component density after the reaction.
- the inventor of the present application has examined the reaction system of nitrogen atoms and NO in detail, and found that the relationship of the formula (6) is established.
- Equation (6) When NO gas is mixed with a gas containing nitrogen atoms, various reactions occur between the nitrogen atoms, NO, and the dilution gas, and equilibrium is reached after a certain period of time.
- the reaction when NO gas was mixed with the nitrogen atom-containing gas was simulated, and the component densities before and after the reaction were compared.
- An engineering equalization solver F-Chart Software
- M means a third body and corresponds to any particle type appearing in the reaction system.
- N + N + M ⁇ N 2 + M K 7 1.22 ⁇ 10 ⁇ 32 (cm 6 / s) (7)
- N + O + M ⁇ NO + M K 8 9.80 ⁇ 10 ⁇ 33 (cm 6 / s) (8)
- N + O 2 ⁇ NO + O K 9 1.11 ⁇ 10 ⁇ 16 (cm 3 / s) (9)
- N + O 3 ⁇ NO + O 2 K 10 1.00 ⁇ 10 ⁇ 16 (cm 3 / s) (10)
- N + NO ⁇ N 2 + OK 11 2.94 ⁇ 10 ⁇ 11 (cm 3 / s) (11)
- N + NO 2 ⁇ N 2 O + OK 12 1.21 ⁇ 10 ⁇ 11 (cm 3 / s) (12)
- O + O + M ⁇ O 2 + M K 13 1.05 ⁇ 10 ⁇ 33 (cm 6 / s) (13)
- O + O 2 + N ⁇ O 3 + M K 14 5.88 ⁇ 10 ⁇ 34 (c
- the nitrogen atom density can be calculated by the equation (6) by mixing NO gas having a known density with the nitrogen atom-containing gas and measuring the density of NO and NO 2 after the reaction. Further, since this reaction reaches equilibrium in an extremely short time of about 1 millisecond, the nitrogen atom density at the NO gas mixing point can be substantially measured. Further, since the density of each component hardly changes after reaching the equilibrium from FIG. 2, even if it takes time to measure NO and NO 2 , there is no problem in calculating the nitrogen atom density. Further, when NO having a known density is supplied and the densities of NO and NO 2 after the reaction are continuously measured, the nitrogen atom density can be calculated in real time from the equation (6).
- the measurement method of the present invention is intended to measure the nitrogen atom density in the nitrogen atom-containing gas.
- a certain value is assumed as the initial nitrogen atom density [N] 0 and this is used as the initial condition for the chemical reaction.
- Perform a simulation Thereby, the density of NO and NO 2 after the reaction is obtained, and the nitrogen atom density is calculated from the equation (6).
- the nitrogen atom density given as the initial value and the nitrogen atom density calculated from the equation (6) coincide.
- Equation (6) the range of the nitrogen atom density that can be measured by Equation (6) will be described.
- the measurement accuracy of NO and NO 2 is about 0.1 ppm.
- 0.1 ppm corresponds to a density of about 2.5 ⁇ 10 12 (cm ⁇ 3 ). Therefore, the lower limit of the nitrogen atom density obtained by the equation (6) is about 1 ⁇ 10 12 (cm ⁇ 3 ).
- the nitrogen gas supplied from the nitrogen gas supply source 1 or a mixed gas of nitrogen and rare gas is adjusted to a predetermined flow rate by the flow rate regulator 2a, and then passed through the discharge unit 3 near atmospheric pressure. At this time, a high voltage is applied from the high voltage power supply 4 between a pair of electrodes included in the discharge unit 3 near atmospheric pressure, and discharge is generated in the vicinity of atmospheric pressure.
- a part of the nitrogen gas is dissociated into nitrogen atoms.
- the nitrogen atom-containing gas thus generated flows out from the downstream end of the near-atmospheric pressure discharge unit 3 to the transport pipe 10.
- a part of the nitrogen atom-containing gas flowing out from the downstream end of the near-atmospheric pressure discharge unit 3 is sucked by the pump 6 from the gas suction point 9.
- the flow rate of the intake gas is adjusted by the flow rate controller 2c.
- the NO gas diluted to a predetermined concentration is supplied from the NO gas supply source 5 while a part of the nitrogen atom-containing gas is sucked.
- Nitrogen gas or rare gas is used as the dilution gas.
- the nitrogen atom-containing gas to be measured is diluted by mixing the gases, it is necessary to perform correction after the measurement. In general, it is desirable to use about 1000 ppm of NO, but it is appropriately determined according to the nitrogen atom density to be measured, the intake flow rate of the nitrogen atom-containing gas, and the flow rate of the NO gas.
- the supplied NO gas is adjusted to a predetermined flow rate by the flow rate regulator 2b and then mixed with the sucked nitrogen atom-containing gas at the NO gas mixing point 8.
- the nitrogen atom density is rapidly attenuated by the equation (7), and is attenuated to about 1 ⁇ 10 12 (cm ⁇ 3 ) after 1 second near the atmospheric pressure. Therefore, the NO gas mixing point 8 is set to a position where the transport time from the downstream end of the discharge unit 3 near atmospheric pressure is 1 second or less.
- the concentration of NO and NO 2 is measured by a nitrogen oxide concentration meter 7 installed downstream of the NO gas mixing point 8. As described above, it takes about 1 millisecond in the vicinity of atmospheric pressure until the chemical reaction in the mixed gas reaches equilibrium. Accordingly, the installation position of the nitrogen oxide concentration meter 7 is a position that requires at least 1 millisecond for transportation from the NO gas mixing point 8 in consideration of the intake gas flow rate, the NO gas flow rate, and the pipe diameter. However, the time taken for the chemical reaction to reach equilibrium may exceed 1 millisecond depending on the gas pressure, gas temperature, gas flow rate, and the shape of the piping. It is necessary to determine the position.
- the concentration of NO gas to be supplied is C NO0 (ppm)
- the flow rate is Q NO (cm 3 / s)
- the flow rate of the nitrogen-containing gas to be sucked is Q N (cm 3 / s)
- the NO concentration at the mixing point 8 C NOi (ppm) is obtained from the equation (21).
- the NO concentration C NOm and the NO 2 concentration C NO2m after the reaction are measured by the nitrogen oxide concentration meter 7.
- the target nitrogen atom density can be calculated. Note that, as shown in FIG. 2, the reaction between nitrogen atoms and NO is as fast as about 1 millisecond, so the NO gas mixing point 8 can be regarded as a nitrogen atom density measurement point.
- Embodiment 1 of the present invention a part of the nitrogen atom-containing gas is sucked in, mixed with a predetermined density of NO, and the NO and NO 2 densities after the reaction are measured. 6), the nitrogen atom density can be calculated in real time near atmospheric pressure.
- the nitrogen atom-containing gas is diluted and the nitrogen atom density is lowered. Therefore, in order to calculate the nitrogen atom density strictly, it is necessary to convert the nitrogen atom density obtained by the equation (6) according to the equation (22).
- [N] R is a more accurate nitrogen atom density after conversion
- [N] m is a nitrogen atom density obtained from the equation (6).
- the NO gas flow rate is 1/10 of the nitrogen atom-containing gas flow rate
- the difference between [N] R and [N] m is about 10%. Accordingly, the ratio of the gas flow rate is taken into consideration, and the correction of Expression (22) is performed as necessary.
- Embodiment 1 of the present invention near atmospheric pressure discharge is used for generating nitrogen atoms. This is because high-energy electrons are generated by forming non-equilibrium plasma near atmospheric pressure, and nitrogen molecules are efficiently dissociated. Examples of discharge modes that can generate non-equilibrium plasma near atmospheric pressure include dielectric barrier discharge, atmospheric pressure glow discharge, creeping discharge, and short pulse corona discharge.
- the nitrogen atom measuring method according to the present invention can measure nitrogen atoms generated by any method. Therefore, even in cases other than the above, for example, nitrogen atoms generated by thermal dissociation or electron beam irradiation can be measured by the same method.
- the pump 6 is means for sucking a part of the nitrogen atom-containing gas.
- the flow rate controller 2c is a means for adjusting the flow rate of the nitrogen atom-containing gas to be sucked. Even if these are not used, a mechanism capable of generating a pressure difference and drawing a predetermined flow rate can be substituted. For example, if the transport pipe 10 is in a pressurized state instead of using a pump and a needle valve is used instead of the flow rate controller 2c, a nitrogen atom-containing gas having a desired flow rate can be drawn.
- the nitrogen oxide densitometer 7 used in the first embodiment of the present invention is for measuring the concentration of NO and NO 2 , and includes various methods such as a chemiluminescence type, a zirconia type, and a constant potential electrolytic type. Is used. Any means other than the nitrogen oxide concentration meter can be used as long as it can measure the concentrations of NO and NO 2 . For example, a Fourier transform infrared absorptiometer (FTIR), a mass analyzer, a gas chromatography and the like can be applied.
- FTIR Fourier transform infrared absorptiometer
- the concentration of NO and NO 2 is independently measured by the nitrogen oxide meter 7, but by measuring the total nitrogen oxide concentration [NO x ] m which is the sum of both, The nitrogen atom density can also be obtained. Then, equation (6) is rewritten by equation (23)
- the nitrogen atom density at the time of a process target arrival is predictable by setting the position of the gas mixing point 8 appropriately.
- the distance from the gas intake point 9 to the object to be treated is L 1
- the cross-sectional area of the transport pipe 10 is S 1
- the gas flow rate is Q 1
- the pressure in the pipe is P 1
- the gas temperature is T 1 .
- the distance from the gas intake point 9 to the gas mixing point 8 is L 2
- the cross-sectional area of the measurement gas transport pipe 11 is S 2
- the gas flow rate is Q 2
- the pipe pressure is P 2
- the gas temperature is T 2 .
- L 2 is determined according to equation (24).
- the time until the nitrogen atom-containing gas reaches the object to be treated is equal to the time until the nitrogen atom-containing gas reaches the NO gas mixing point 8, that is, the nitrogen atom density measurement point, and the measured nitrogen atoms
- the density is equal to the nitrogen atom density when the object to be processed is reached.
- L 2 L 1 ⁇ (Q 2 ⁇ S 1 ⁇ P 1 ⁇ T 2 ) / (Q 1 ⁇ S 2 ⁇ P 2 ⁇ T 1 ) (24)
- Equation (24) By using a system that satisfies Equation (24), it is possible to indirectly determine the density of nitrogen atoms that reach the processing target, and to effectively control the processing time and processing conditions.
- Embodiment 1 of the present invention a part of the nitrogen atom-containing gas generated by the discharge is sucked and measurement is performed.
- it can also be achieved by directly mixing the NO gas with the nitrogen atom-containing gas flowing through the transport pipe 10.
- the remote plasma treatment cannot be performed.
- FIG. FIG. 4 is a block diagram showing a configuration of a nitrogen atom measuring apparatus to which the nitrogen atom measuring method according to Embodiment 2 of the present invention is applied.
- the nitrogen atom measuring apparatus according to the second embodiment of the present invention differs from the nitrogen atom measuring apparatus according to the first embodiment of the present invention in the number of locations where the NO gas is mixed, and the other portions are the same.
- the same reference numerals are given to the portions, and the description is omitted.
- NO gas is mixed at only one point of the NO gas mixing point 8, but in the nitrogen atom measuring apparatus according to the second embodiment of the present invention, the measurement gas
- the NO gas mixing points 8a, 8b and 8c along the transport pipe 11 are mixed at three points.
- bulb 12a, 12b, 12c for switching a NO gas supply flow path is each arrange
- the operation of the nitrogen atom measuring apparatus according to Embodiment 2 of the present invention will be described.
- the process up to the point where the nitrogen atom-containing gas is sucked at a predetermined flow rate from the gas suction point 9 using the pump 6 is the same as in the first embodiment.
- the valve 12b and the valve 12c are closed, only the valve 12a is opened, and NO gas is supplied. Thereby, the nitrogen atom density at the NO gas mixing point 8a is measured.
- only the valve 12b is opened and NO gas is supplied.
- the nitrogen atom density at the NO gas mixing point 8b is measured.
- only the valve 12c is opened and NO gas is supplied. Thereby, the nitrogen atom density at the NO gas mixing point 8c is measured.
- the nitrogen atom density at three different points was measured along the gas flow in the measurement gas transport pipe 11.
- the time to reach the NO gas mixing point that is, the transport time can be calculated from the gas flow rate and the distance from the downstream end of the discharge unit 3 near atmospheric pressure to the NO gas mixing points 8a, 8b, 8c.
- the attenuation characteristic of the nitrogen atom density can be obtained.
- the nitrogen atom densities measured at the NO gas mixing points 8a, 8b, and 8c are Na, Nb, and Nc, respectively, and the transport times to the respective NO gas mixing points 8a, 8b, and 8c are Ta, Tb, and Tc.
- the relationship between nitrogen atom density and transport time is plotted.
- equation (7) when only equation (7) is considered as the decay process of nitrogen atoms, the theoretical formula for nitrogen atom density decay is equation (25).
- k r (cm 6 / s) is a spatial recombination rate coefficient.
- [M] is the density of the third body, and is calculated from the pressure and temperature.
- the nitrogen atom-containing gas generated by the discharge is carried downstream by a stainless steel tube having an inner diameter of 4.35 mm.
- the NO gas mixing points 8a, 8b and 8c are located 40 mm, 100 mm and 160 mm downstream from the outlet of the near atmospheric pressure discharge unit 3, respectively.
- NO gas having a concentration of 1000 ppm diluted with nitrogen is added to the discharge downstream gas at a flow rate of 100 to 300 cc per minute.
- FTIR is used for the measurement of NO and NO 2 .
- the supplied NO concentration and the measured NO and NO 2 concentrations are converted into densities, respectively, and the nitrogen atom density at each NO gas mixing point 8a, 8b, 8c is calculated by equation (6).
- FIG. 5 shows various conditions and actual measurement data in the experimental example.
- the measured concentrations of NO and NO 2 were about 10 ppm and 2 ppm, respectively, and the nitrogen atom density was about 10 14 (cm ⁇ 3 ).
- Equation (25) is 2.3 ⁇ 10 19 (cm ⁇ 3 ).
- the nitrogen atom density is measured at a plurality of locations, the attenuation characteristics of the nitrogen atoms are acquired from the relationship with the transport time, and nitrogen at a point other than the NO gas mixing point is obtained based on this.
- the atomic density can be estimated.
- the above-mentioned nitrogen atom density decay characteristics consider only spatial recombination and do not include other nitrogen atom annihilation processes such as surface recombination. Therefore, it is necessary to correct Expression (25) depending on the material and shape of the transport pipe. In particular, when a thin tube is used as a transport tube, the influence of surface recombination becomes relatively large.
- three NO gas mixing points are used, but the same method can be used as long as the number is two or more.
- FIG. 7 is a block diagram showing a configuration of a plasma processing apparatus according to Embodiment 3 of the present invention.
- the plasma processing apparatus according to the third embodiment of the present invention is a plasma processing apparatus in which the processing chamber 14 is arranged on the downstream side of the nitrogen atom measuring apparatus according to the first embodiment of the present invention.
- the measurement results are collected from the nitrogen oxide concentration meter 7, and based on the measurement results, the nitrogen gas supply source 1, the flow controller 2a, the high voltage power source 4 or the like is provided.
- a processing chamber 14 is connected to the tip of the transport tube 10 extending from the outlet of the near-atmospheric pressure discharge unit 3. And the nitrogen atom containing gas produced
- the nitrogen oxide concentration meter 7 measures the concentrations of NO and NO 2 by the method shown in the first embodiment.
- the sequencer 13 receives the data measured by the nitrogen oxide densitometer 7 and calculates the nitrogen atom density by performing an operation taking into account the equation (6) and, if necessary, the equation (22). Then, the sequencer 13 controls the nitrogen gas supply source 1, the flow rate regulator 2 a, the high voltage power supply 4, a pressure regulator and a temperature regulator (not shown) based on the calculated nitrogen atom density.
- the composition of the nitrogen gas supplied to the near-atmospheric-pressure discharge unit 3, the flow rate of the nitrogen gas, the discharge power, the gas temperature, the pressure, or a plurality thereof is adjusted.
- the nitrogen atom density and the nitrogen atom flux suitable for the process are adjusted, and the nitrogen atom-containing gas is supplied to the processing chamber 14.
- the nitrogen atom density is measured in real time, and the discharge chamber is controlled according to the measurement result, so that the processing chamber is maintained in a state where the desired nitrogen atom density is maintained.
- 14 can be supplied with a nitrogen atom-containing gas.
- it is possible to realize a process controlled with high accuracy by changing the nitrogen atom density and the nitrogen atom flux with time in a form suitable for processing.
- the outlet of the near atmospheric pressure discharge unit 3 and the processing chamber 14 be as close as possible.
- the nitrogen atom density is attenuated to at least about 1 ⁇ 10 12 (cm ⁇ 3 ), and the efficiency at the time of forming a nitride film and other processes is lowered. . Therefore, the processing chamber 14 is installed at a position where the transport of the nitrogen atom-containing gas is within 1 second, preferably within 0.1 second. Further, in order to supply nitrogen atoms to the processing chamber 14 with a high flux, it is necessary to reduce the flow rate of air sucked from the gas intake point 9 into the measurement unit as much as possible. On the other hand, the lower limit of the flow rate of the intake air in the measuring unit is determined by the required flow rate for measuring the NO and NO 2, usually per minute about one liter.
- sequencer 13 is used as the calculation and control means in the third embodiment. Any means other than the sequencer can be used as long as it can calculate the nitrogen atom density from the calculation based on the equation (6) and can control the above-described conditions such as the discharge power based on the obtained nitrogen atom density. Further, although the sequencer 13 has both the calculation means and the control means, these may be made independent.
- Nitrogen gas supply source 2a, 2b, 2c Flow rate regulator, 3 Near atmospheric pressure discharge unit, 4 High voltage power supply, 5 Gas supply source, 6 Pump, 7 Nitrogen oxide concentration meter, 8, 8a, 8b, 8c gas Mixing point, 9 gas intake point, 10 transport pipe, 11 measuring gas transport pipe, 12a, 12b, 12c valve, 13 sequencer, 14 processing chamber.
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Abstract
Description
O+N+M→NO(B2Π)+M→NO+M+hν (2)
窒素原子の量がNOの量より小さいとき、
O+NO+M→NO2(A2B1)+M→NO2+M+hν (3)
また、一酸化窒素ガス滴定法の窒素原子密度測定方法は、大気圧近傍での比較的簡易な窒素原子密度測定が可能であるが、NO供給量を変化させて滴定点を見出す必要があることから、リアルタイム測定は実現できない。
以下の実施の形態の説明では表記[X]を用いて粒子種Xの数密度(cm-3)を表すこととする。一方、NO測定などでは、濃度CX(ppm)を用いる方が都合が良い。圧力をP(kPa)、ガス温度をT(K)とすれば、数密度[X]と濃度CXは、式(4)の関係で互いに変換可能である。なお、NAはアボガドロ数6.02×1023(mol-1)である。
この発明の実施の形態1に係る窒素原子測定装置では、窒素ガス供給源1と、窒素ガス流量調節手段である流量調節器2aと、大気圧近傍放電ユニット3によって、窒素原子含有ガスが生成され、輸送管10によって輸送される。ここで、窒素ガス供給源1からは、純窒素ガス、あるいは窒素ガスと希ガスが所定の割合で混合されたガスを供給する。
大気圧近傍放電ユニット3は、一対の電極を内包しており、高電圧電源4が接続されている。
窒素原子計測部は、NOガス供給源5と、NOガス流量調節手段である流量調節器2bと、窒素原子含有ガスの一部を吸気する手段であるポンプ6と、窒素原子含有ガスの流量調節手段である流量調節器2cと、NO及びNO2濃度を測定する窒素酸化物濃度計7からなる。
NOガス供給源5からは、窒素ガスあるいは希ガスにより所定濃度に希釈されたNOガスを供給する。ガス吸気点9は大気圧近傍放電ユニット3の下流に位置し、ガス吸気点9にて測定ガス輸送管11が分岐している。NOガス混合点8は測定ガス輸送管11に存在し、流量調節器2cと窒素酸化物濃度計7は、共に測定ガス輸送管11のNOガス混合点8より下流側に位置する。
窒素原子を含むガスにNOガスを混合した場合、窒素原子、NOおよび希釈ガス間で種々反応が生じ、一定時間経過後に平衡に至る。式(7)~(20)に示す14通りの反応式を考慮することで、窒素原子含有ガスにNOガスを混合した際の反応をシミュレーションし、反応前後の成分密度を比較した。シミュレーションにはEngineering Eqartion Solver(F-Chart Software)を使用した。また、各反応の速度係数はいずれもNational Institute of Standards and technology(NIST)のChemical Kinetic Databaseより引用した。ここで、Mは第三体を意味し、上記反応系で現れるあらゆる粒子種に対応する。
N+O+M→NO+M K8=9.80×10-33(cm6/s) (8)
N+O2→NO+O K9=1.11×10-16(cm3/s) (9)
N+O3→NO+O2 K10=1.00×10-16(cm3/s) (10)
N+NO→N2+O K11=2.94×10-11(cm3/s) (11)
N+NO2→N2O+O K12=1.21×10-11(cm3/s) (12)
O+O+M→O2+M K13=1.05×10-33(cm6/s) (13)
O+O2+N→O3+M K14=5.88×10-34(cm6/s) (14)
O+O3→O2+O2 K15=7.96×10-15(cm3/s) (15)
O+NO+M→NO2+O2 K16=8.84×10-32(cm6/s) (16)
O+NO2→NO+O2 K17=9.73×10-12(cm3/s) (17)
O2+NO+NO→NO2+NO2 K18=1.93×10-38(cm6/s) (18)
O3+NO→O2+NO2 K19=1.82×10-14(cm3/s) (19)
O3+NO2→NO3+O2 K20=3.23×10-17(cm3/s) (20)
図2の化学反応シミュレーション結果から、窒素原子密度はNOガスとの混合後急激に低下し、1ミリ秒程度でほぼ消滅することが分かる。また、供給した一酸化窒素の密度は減少する一方で、二酸化窒素が発生する。
また、この反応は1ミリ秒程度と、極めて短時間で平衡に至るため、実質的にNOガス混合点での窒素原子密度を測定できる。
また、図2より平衡到達後は各成分の密度はほとんど変化しないため、NOとNO2の計測に時間を要しても、窒素原子密度算出のうえで問題とはならない。
また、密度が既知のNOを供給して、反応後のNOとNO2の密度を連続的に測定すれば、式(6)よりリアルタイムに窒素原子密度を算出することが可能である。
本願発明の測定法は、窒素原子含有ガス中の窒素原子密度を測定することが目的となるが、ここではある値を初期窒素原子密度[N]0として仮定し、これを初期条件として化学反応シミュレーションを実施する。これにより、反応後のNOとNO2の密度を求め、式(6)から窒素原子密度を算出する。本窒素原子測定原理が成立する条件では、初期値として与えた窒素原子密度と、式(6)から算出される窒素原子密度は一致することになる。
図3に示す結果から、[NO]inが[N]0を超えている条件において、式(6)から求まる窒素原子密度は、初期条件として与えた窒素原子密度と極めてよく一致し、従って、[N]と[N]0はほぼ等しいという関係が成り立つことが分かる。
また、この特性は、初期窒素原子密度[N]0が変わっても、同様に成立することが分かる。
現在、一般に入手可能な装置を用いた場合、NO及びNO2の測定精度は0.1ppm程度である。大気圧において0.1ppmは、2.5×1012(cm-3)程度の密度に対応する。従って、式(6)により求められる窒素原子密度の下限は、1×1012(cm-3)程度である。
最初に、窒素原子含有ガスの生成部を説明する。
窒素ガス供給源1から供給される窒素ガス、あるいは窒素と希ガスの混合ガスを、流量調節器2aによって所定の流量に調節したうえで、大気圧近傍放電ユニット3を通過させる。このとき、大気圧近傍放電ユニット3に内包される一対の電極間に、高電圧電源4から高電圧を印加し、大気圧近傍で放電を発生させる。窒素ガスは、放電空間を通過する際、その一部が解離されて窒素原子となる。こうして発生した窒素原子含有ガスは、大気圧近傍放電ユニット3の下流側端部から輸送管10に流出する。
大気圧近傍放電ユニット3の下流側端部から流出した窒素原子含有ガスの一部を、ガス吸気点9から、ポンプ6によって吸気する。吸気するガス流量は、流量調節器2cによって調節する。窒素原子含有ガスの一部を吸気している状態で、NOガス供給源5から所定濃度に希釈されたNOガスを供給する。希釈ガスとしては、窒素ガスあるいは希ガスを用いる。供給するNOの濃度が高いと、供給流量を小さくする必要があり、窒素原子含有ガスとの混合に時間を要する結果となる。一方NO濃度が低いと、供給流量を大きくする必要があり、NOガス消費量が増大する。
一方、本発明による窒素原子測定法は、いかなる方法で発生した窒素原子であっても測定可能である。従って、上記以外であっても、例えば熱解離や電子ビーム照射によって生成された窒素原子であっても、同様の方法で測定できる。
図4は、この発明の実施の形態2に係る窒素原子測定方法を適用した窒素原子測定装置の構成を示すブロック図である。
この発明の実施の形態2に係る窒素原子測定装置は、この発明の実施の形態1に係る窒素原子測定装置とNOガスを混合する箇所の数が異なり、それ以外は同様であるので、同様な部分に同じ符号を付記し説明は省略する。
この発明の実施の形態1に係る窒素原子測定装置では、NOガスがNOガス混合点8の一点のみで混合しているが、この発明の実施の形態2に係る窒素原子測定装置では、測定ガス輸送管11に沿ったNOガス混合点8a、8b、8cの3点で混合している。
そして、NOガス供給流路を切り替えるためのバルブ12a、12b、12cを、それぞれ流量調節器2bとNOガス混合点8a、8b、8cの間に配備する。
ポンプ6を用いて、ガス吸気点9より窒素原子含有ガスを所定流量吸気するところまでは、実施の形態1と同様である。実施の形態2では、まずバルブ12bとバルブ12cを閉じ、バルブ12aのみを開放し、NOガスを供給する。これにより、NOガス混合点8aでの窒素原子密度を測定する。
次に、バルブ12bのみを開放し、NOガスを供給する。これにより、NOガス混合点8bでの窒素原子密度を測定する。
次に、バルブ12cのみを開放し、NOガスを供給する。これにより、NOガス混合点8cでの窒素原子密度を測定する。これにより、測定ガス輸送管11のガス流に沿って、異なる3点での窒素原子密度を測定したことになる。
NOガス混合点8a、8b、8cからNOガスを混合して測定した窒素原子密度Na、Nb、Ncと輸送時間Ta、Tb、Tcを用いて、式(25)に対する回帰分析を実施することで、式(25)における[N]0とkrが求まる。ここで、[N]0は大気圧近傍放電ユニット3出口での窒素原子密度である。
また、求まった[N]0とkr値を式(25)に代入することで、窒素原子密度の時間変化を与える関係が得られる。これにより、測定点以外での窒素原子密度を見積もることができる。
毎分10リットル(10slm)の窒素ガスを大気圧近傍放電ユニット3に供給する。大気圧近傍放電ユニット3内では、電極間隔1mm、長さ120mmの一対の電極に交流高電圧を印加し、大気圧下の誘電体バリア放電によって窒素原子を発生させる。高電圧電源4からは、周波数4.5kHz、印加電圧約6.5kV0-pの交流電圧を出力する。
供給NO濃度と、測定されたNOおよびNO2濃度を、それぞれ密度に換算し、式(6)により各NOガス混合点8a、8b、8cにおける窒素原子密度を算出する。
NO及びNO2の実測濃度はそれぞれ10ppm、2ppm程度、窒素原子密度は1014(cm-3)程度であった。3箇所での測定から得られた窒素原子減衰特性を図6に示す。縦軸に窒素原子密度を、横軸にはNOガス混合点までの輸送時間tを示す。減衰の理論式との比較から、t=0での窒素原子密度[N]0=4.1×1014(cm-3)、再結合速度係数kr=9.2×10-33(cm6/s)と求まった。ここで、圧力を101.3kPa、ガス温度を323Kとすると、式(25)中の[M]=2.3×1019(cm-3)である。これらの値を式(25)に代入すると、窒素原子密度減衰の式として、式(26)が得られる。
上述の窒素原子密度減衰特性には空間再結合のみを考慮し、表面再結合など、その他の窒素原子消滅過程は含めていない。従って、輸送管の材料や形状によっては、式(25)に補正を施す必要がある。特に、細い管を輸送管として用いると、表面再結合の影響が相対的に大きくなる。
なお、実施の形態2では、NOガス混合点を3箇所としているが、2箇所以上であれば同様の方法を用いることができる。
図7は、この発明の実施の形態3に係るプラズマ処理装置の構成を示すブロック図である。
この発明の実施の形態3に係るプラズマ処理装置は、この発明の実施の形態1に係る窒素原子測定装置の下流側に処理室14を配置したプラズマ処理装置である。
そして、この発明の実施の形態1に係る窒素原子測定装置には、窒素酸化物濃度計7から測定結果を収集し、測定結果に基づいて窒素ガス供給源1、流量調節器2a、高電圧電源4などを制御するシーケンサ13が備えられている。
大気圧近傍放電ユニット3の出口から延びる輸送管10の先端には処理室14が接続されている。そして、大気圧近傍放電ユニット3で生成された窒素原子含有ガスは、輸送管10を通過して処理室14に導かれ処理に利用される。
まず、実施の形態1に示した方法で、窒素酸化物濃度計7でNOとNO2の濃度を測定する。シーケンサ13では、窒素酸化物濃度計7で測定されたデータを受信し、式(6)、必要に応じて式(22)も加味した演算を行い、窒素原子密度を算出する。
それから、シーケンサ13は、算出された窒素原子密度に基づいて、窒素ガス供給源1、流量調節器2a、高電圧電源4、図示しない圧力調節器や温度調節器を制御する。これにより、大気圧近傍放電ユニット3に供給される窒素ガスの組成、窒素ガスの流量、放電電力、ガス温度、圧力のいずれか、あるいは複数を調節する。これにより、プロセスに適した窒素原子密度、窒素原子フラックスに調節し、処理室14に窒素原子含有ガスを供給する。
また、処理に適した形で窒素原子密度や窒素原子フラックスを時間的に変化させ、高精度で制御されたプロセスが実現できる。
また、処理室14に高いフラックスで窒素原子を供給するには、ガス吸気点9から測定部に吸気される流量をできるだけ少なくする必要がある。
一方、測定部に吸気される流量の下限値は、NO及びNO2を測定するための必要流量で決まり、通常は毎分1リットル程度である。
また、シーケンサ13に演算手段と制御手段を併せ持たせているが、これらを独立にしてもよい。
Claims (9)
- 大気圧近傍で窒素原子の密度を測定する窒素原子測定方法であって、
窒素原子発生源で発生した窒素原子含有ガスのうち所定量に対し、上記窒素原子発生源の下流において、濃度が既知の所定量の一酸化窒素ガスを混合する手順と、
上記窒素原子含有ガスと混合された上記一酸化窒素ガスの反応後に、一酸化窒素の密度と二酸化窒素の密度を測定する手順と、
窒素原子密度は上記一酸化窒素ガスの既知の濃度から測定した上記一酸化窒素の濃度と測定した上記二酸化窒素の濃度との和を減算して得る差であるという関係を用いて窒素原子密度を算出する手順と、
を有することを特徴とする窒素原子測定方法。 - 上記窒素原子含有ガス中の窒素原子密度が、1×1012(cm-3)以上であることを特徴とする請求項1に記載の窒素原子測定方法。
- 上記一酸化窒素ガスの既知の濃度が上記窒素原子密度に対する比が1を超え且つ100未満であることを特徴とする請求項1または2に記載の窒素原子測定方法。
- 上記窒素原子含有ガスが上記窒素原子発生源を流出してから、上記一酸化窒素ガスが混合するまでの時間が、1秒以下であることを特徴とする請求項1乃至3のいずれかに記載の窒素原子測定方法。
- 大気圧近傍で窒素原子の密度を測定する窒素原子測定装置であって、
窒素原子発生源で発生した窒素原子含有ガスのうち所定量に対し、上記窒素原子発生源の下流から吸気する手段と、
上記吸気された窒素原子含有ガスを所定流量に調節する流量調節手段と、
濃度が既知の一酸化窒素ガスを供給する一酸化窒素ガス供給源と、
上記供給された一酸化窒素ガスを所定流量に調節する流量調節手段と、
一酸化窒素の密度と二酸化窒素の2密度を計測する計測器と、を備え、
上記吸気された窒素原子含有ガスに対して、上記一酸化窒素ガスを混合した後に、一酸化窒素の密度と二酸化窒素の密度とを測定するとともに、窒素原子密度は上記一酸化窒素ガスの既知の濃度から測定した上記一酸化窒素の濃度と測定した上記二酸化窒素の濃度との和を減算して得る差であるという関係を用いて窒素原子密度を算出することを特徴とする窒素原子測定装置。 - 上記窒素原子含有ガス中の窒素原子密度が、1×1012(cm-3)以上であることを特徴とする請求項5に記載の窒素原子測定装置。
- 上記一酸化窒素ガスの既知の濃度が上記窒素原子密度に対する比が1を超え且つ100未満であることを特徴とする請求項5または6に記載の窒素原子測定装置。
- 上記窒素原子含有ガスが上記窒素原子発生源を流出してから、上記一酸化窒素ガスが混合するまでの時間が、1秒以下であることを特徴とする請求項5乃至7のいずれかに記載の窒素原子測定装置。
- 窒素原子含有ガスを処理対象に接触させることで処理を行なうプラズマ処理装置であって、
上記請求項5乃至8のいずれかに記載の窒素原子測定装置を備えるとともに、上記窒素原子密度が所定の密度となるよう、放電電力、ガス組成、ガス流用、ガス温度、ガス圧力の少なくともいずれか1つを制御する制御手段を備えることを特徴とするプラズマ処理装置。
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WO2015176733A1 (en) | 2014-05-22 | 2015-11-26 | Institut Jožef Stefan | Method and device for detection and measuring the density of neutral atoms of hydrogen, oxygen or nitrogen |
JP2022114415A (ja) * | 2021-01-26 | 2022-08-05 | 富蘭登科技股▲ふん▼有限公司 | スペクトルにより物質の物理的状態を測定する装置及びスペクトルにより物質の物理的状態を測定する方法 |
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CN102066925B (zh) | 2013-07-03 |
JP5295237B2 (ja) | 2013-09-18 |
JPWO2009154037A1 (ja) | 2011-11-24 |
CN102066925A (zh) | 2011-05-18 |
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